CN108003774A - 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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- 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
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- 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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- 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, and specific preparation method is：After the reaction kettle checked is heated up, under nitrogen atmosphere, liquid MDI stirring is added, polyether polyol is added, continues stirring and obtain base polyurethane prepolymer for use as；Then the stirring of some polyesters polyalcohols 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 technology
With the strengthening of people's awareness of environmental protection, various countries' environmental regulation is particularly to volatile organic compounds in coating system
(VOC) the stringent control of content, woodwork coating industry are gradually friendly to environment from the traditional solvent-borne coating of high energy consumption, high pollution
Good, resource-conserving water paint transformation, promotes the development using water paint as the low-contamination type coating of representative.Polyurethane
Coating has excellent wear-resisting, chemical-resistant and toughness, and aqueous polyurethane has that VOC content is low, pollution is small, cost is low, divides
Minor structure Scalability, dilutable water, it is easy to clean the advantages that, its paint film has high, the wear-resistant and good toughness of intensity etc. special
Point, gradually obtains extensive accreditation 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 performance such as richness is poor, chemicals-resistant deficiency, limit it makes as aqueous woodware paint
With, it is necessary to be carried out to it cross-linking modified, epoxide 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
The nano composite inorganic antiseptic mixing prepared with the prefabricated colloidal sol of organic expander soil of nano silicon dioxide, 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, defoamer
Slurry is mixed into levelling agent, and ground filtering packing, is prepared nano antibacterial water woodenware paint, and the aqueous woodware paint is by three
The mixing of kind of resin emulsion different proportion be used as film forming matter, not only reduces cost, and ensure woodcare paint with low VOC values,
It is anti-be adhered, the characteristics of damage resistant, anti-pollution, color inhibition and closure are good, and a variety of inorganic nano components contained assign water-based
The advantages of woodcare paint broad-spectrum antiseptic and lasting antibacterial, a variety of nano multifunctional assistants of selection are all Diamond Search and inorganic product,
Assigning, aqueous woodware paint is functional at the same time, ensures the environmentally protective performance of product, but product needs to add in preparation process
Solubilizer, the solid content of product is low, and using effect is limited.It is a kind of environmentally friendly disclosed in Chinese patent CN 105482587B
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, coalescents, emulsifying agent, crosslinking agent, dispersant, defoamer, other
Auxiliary agent and deionized water, the film forming agent of woodcare paint prepared by this method is 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 there is stability
Well, hardness is big, stain resistant performance is good, nontoxic the advantages of having no irritating odor.From the above-mentioned prior art, nano modification
Woodcare paint containing polyurethane can assign the multiple functions such as woodcare paint flame-proof antibiotic enhancing, but be 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
Being mixed with sold resin lotion simple physical to improve performance, nano material is difficult to infiltrate through in the resin macromolecular of molecular weight,
Gathering for nano material is be easy to cause, directly affects the performance and stability of product.
The content 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
Preparation method, prefabricated nanometer additive is added in the preparation process of polyurethane aqueous woodcare paint, nanometer has both been improved and has added
Add dispersiveness of the agent in polyurethane aqueous woodcare paint, and nanometer additive can be used as aggregate and crystalline structure, promote poly- ammonia
Ester large molecule forms regular oriented structure around nanometer additive, is conducive to improve the film forming of 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, it is characterised 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, its feature exists
In：Comprise the following steps：
(1) reaction kettle air-tightness, agitating paddle and kettle wall cleanliness factor are checked, it is ensured that totally protect valve without steam and water droplet in kettle
Door is closed, and feeding port is opened, and filter installation is correct, stand-by；
(2) temperature adjustment for the reaction kettle for having checked step (1) is to 65 DEG C, and under nitrogen atmosphere, addition is preheated to 40
DEG C liquid MDI, stir 10-15min under 60-100r/min, add prefabricated polyether polyol, with the speed of 45-60r/min
Continue to stir 10-15min, obtain 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,
It is stand-by；
(4) some polyesters polyalcohol is first added in the base polyurethane prepolymer for use as preparing step (2), with 45-60r/mi n's
Speed continues to stir 10-15min, then adds prefabricated additive prepared by step (3), is evacuated to absolute pressure 20mbar, rises
Temperature is continued to stir 50-60min with the speed of 45-60r/min, is eventually adding remaining polyester polyol, vacuum shape to 80-85 DEG C
Under state, continue to stir 1-2h, discharging with the speed of 50-80r/min, detection nco value obtains nano material and change to 5.5-6.5%
The no-solvent polyurethane woodcare paint of property.
As the preferred of above-mentioned technical proposal, in the step (2), MDI 4,4 '-methyl diphenylene diisocyanate,
One kind or its mixture in 2,4 '-methyl diphenylene diisocyanate and 2,2 '-methyl diphenylene diisocyanate.
As the preferred of above-mentioned technical proposal, in the step (2), MDI is by TDI, IPDI, modified MDI, HDI, XDI,
PAPI is replaced.
As the preferred of above-mentioned technical proposal, in the step (2), the molecular weight of prefabricated polyether polyol is 2600-
3000。
As the preferred of above-mentioned technical proposal, in the step (3), phosphoric acid is that the analysis of 100-300PPM is pure.As upper
State the preferred of technical solution, in the step (3), stand-by timeliness is less than 20min.
As the preferred of above-mentioned technical proposal, in the step (4), some polyesters polyalcohol and remaining polyester polyol
Mass ratio is 1:2.5-3.
As the preferred of above-mentioned technical proposal, 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 the preferred of above-mentioned technical proposal, in the step (4), nano-material modified no-solvent polyurethane woodcare paint
Component, by weight, including 39 parts of MDI, prefabricated 10 parts of polyether polyol, 48 parts of polyester polyol, prefabricated additive 3
Part, total amount is 100 parts.
Compared with prior art, the invention has the advantages that：
(1) MDI, prefabricated polyether polyols are included in nano-material modified no-solvent polyurethane woodcare paint prepared by the present invention
Alcohol, polyester polyol and prefabricated additive, 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.
(2) MDI, prefabricated polyether polyols are included in nano-material modified no-solvent polyurethane woodcare paint prepared by the present invention
Alcohol, polyester polyol and prefabricated additive, wherein prefabricated additive include phosphoric acid, silane coupling agent, neopentyl glycol, polybutene,
Nano carbon white and nano-titanium dioxide, phosphoric acid can prevent the too fast polymerizations of MDI, play inhibition, 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 will not produce carbon dioxide, therefore when curing by the use of micro-moisture in air as crosslinking accelerator
Lacquer painting will not be caused to have bubble, influence the mechanical performance and cosmetic look of coating, neopentyl glycol passes through in addition as plasticizer
Add nano-titanium dioxide and nano silicon dioxide (Nano carbon white) is used as nano modifier, the activity of nano-titanium dioxide
Height, easily reunites, nano silicon dioxide is cooperateed with use with nano-titanium dioxide, nano silicon dioxide can be deposited on nano-silica
Change the surface of titanium, reduce the activity of nano-titanium dioxide, and nano silicon dioxide and nano-titanium dioxide are in silane coupling agent
Under effect, the compatibility performance with MDI and polyurethane is improved, promotes nano silicon dioxide and nano-titanium dioxide surface more
With the group in MDI and polyurethane bonding action occurs for hydroxyl, forms three-dimensional net structure in polyurethane aqueous woodcare paint, carries
The compactness of polyurethane aqueous woodcare paint, heat endurance, ultraviolet light, ageing-resistant, hydrolysis and wear-resisting property after high solidification, and
Nano material adds in the preparation process of polyurethane, and compared with traditional be simply mixed, the present invention first promotes a small amount of poly- ammonia
Lipase absobed, is then added into nano material, reduces scattered difficulty of the nano material in polyurethane and the possibility reunited, makes
Nano material is disperseed more uniformly, and in the building-up process of polyurethane afterwards, promotes polyurethane as skeleton and crystalline structure
Molecule is aligned in nano-material surface, further improves 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, stored and do not had any solvent to volatilize using process, and in work progress, nontoxic to environment and construction personnel,
Prepare and also very easy using process, controllability is strong, and the excellent performance of product, function is more, belongs to high-quality polyurethane water
Property woodcare paint, is suitable for large-scale industrial production, good in economic efficiency.
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 diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and 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
It is stand-by to prefabricated additive, it is ensured that to be added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without aqueous vapor, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
10min is stirred under 60r/min, adds polyether polyol, continues to stir 10min with the speed of 45r/min, obtains polyurethane prepolymer
Body, will first add some polyesters polyalcohol PE1000 in base polyurethane prepolymer for use as, continue to stir 10min with the speed of 45r/min, so
The prefabricated additive added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, continues to stir with the speed of 45r/min
50min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the speed 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 diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and 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
It is stand-by to prefabricated additive, it is ensured that to be added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
15min is stirred under 100r/min, adds polyether polyol, continues to stir 15min with the speed of 60r/min, it is pre- to obtain polyurethane
Aggressiveness, will first add some polyesters polyalcohol PE1000 in base polyurethane prepolymer for use as, continue to stir 15min with the speed of 60r/min,
Then the prefabricated additive added, is evacuated to absolute pressure 20mbar, is warming up to 85 DEG C, continues to stir with the speed of 60r/min
60min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 2h with the speed 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 diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and 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
It is stand-by to prefabricated additive, it is ensured that to be added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
13min is stirred under 80r/min, adds polyether polyol, continues to stir 13min with the speed of 50r/min, obtains polyurethane prepolymer
Body, will first add some polyesters polyalcohol PE1000 in base polyurethane prepolymer for use as, continue to stir 12min with the speed of 55r/min, so
The prefabricated additive added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 83 DEG C, continues to stir with the speed of 50r/min
55min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1.5h with the speed of 60r/min, goes out
Material, detection nco value obtain nano-material modified no-solvent polyurethane woodcare paint to 6%.
Embodiment 4：
(1) by 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and is preheated to 40 DEG C of liquid storages.
(2) nanometer titanium dioxide and molecular weight are spun into 673 armorphous saturated polyester resins 1 for 17,000 Japan：1 kneading point
Dissipate, gas-phase silica then add it is common mediate 30 minutes, will mediate expect to add 0.001% phosphoric acid, 17% silane coupling agent,
The 45 DEG C of storages that cool down in 72.999% neopentyl glycol, 5.6% polybutene after 90 DEG C of high speed dispersions dissolving stirring 1h of heating obtain pre-
Additive processed, it is stand-by, it is ensured that to be added in 20min.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
13min is stirred under 70r/min, adds polyether polyol, continues to stir 13min with the speed of 50r/min, obtains polyurethane prepolymer
Body, will first add some polyesters polyalcohol PE1000, continues to stir with the speed of 45-60r/min in base polyurethane prepolymer for use as
10min, the prefabricated additive then added, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, is continued with the speed of 60r/min
50min is stirred, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the speed of 80r/min,
Discharging, detection nco value obtain nano-material modified no-solvent polyurethane woodcare paint to 5.9%.
Embodiment 5：
(1) by 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, aerosil and polyether polyol (2600 molecular weight), silane coupling agent is jointly pre-
Mixed, the high speed dispersion at a temperature of the speed of 2500r/min and 45 DEG C, is made prefabricated additive, stand-by, it is ensured that to be thrown in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
15min is stirred under 100r/min, adds polyether polyol, continues to stir 15min with the speed of 60r/min, it is pre- to obtain polyurethane
Aggressiveness, will first add some polyesters polyalcohol PE1000 in base polyurethane prepolymer for use as, continue to stir 10min with the speed of 45r/min,
Then the prefabricated additive added, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, continues to stir with the speed of 45r/min
50min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the speed 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, aerosil and polyether polyol (2600 molecular weight), silane coupling agent is jointly pre-
Mixed, the high speed dispersion at a temperature of the speed of 2500r/min and 45 DEG C, is made prefabricated additive, stand-by, it is ensured that to be thrown in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
14min is stirred under 90r/min, adds polyether polyol, continues to stir 13min with the speed of 50r/min, obtains polyurethane prepolymer
Body, will first add some polyesters polyalcohol PE1000 in base polyurethane prepolymer for use as, continue to stir 10min with the speed of 50r/min, so
The prefabricated additive added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 85 DEG C, continues to stir with the speed of 45r/min
60min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 2h with the speed 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 diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, aerosil and polyester polyol (2600 molecular weight), silane coupling agent is jointly pre-
Mixed, the high speed dispersion at a temperature of the speed of 2500r/min and 45 DEG C, is made prefabricated additive, stand-by, it is ensured that to be thrown in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
14min is stirred under 90r/min, adds polyether polyol, continues to stir 14min with the speed of 55r/min, obtains polyurethane prepolymer
Body, will first add some polyesters polyalcohol PE1000 in base polyurethane prepolymer for use as, continue to stir 15min with the speed of 45r/min, so
The prefabricated additive added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, continues to stir with the speed of 60r/min
50min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the speed 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 diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, aerosil and polyester polyol (2600 molecular weight), silane coupling agent is jointly pre-
Mixed, the high speed dispersion at a temperature of the speed of 2500r/min and 45 DEG C, is made prefabricated additive, stand-by, it is ensured that to be thrown in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
13min is stirred under 90r/min, adds polyether polyol, continues to stir 14min with the speed of 50r/min, obtains polyurethane prepolymer
Body, will first add some polyesters polyalcohol PPG2000 in base polyurethane prepolymer for use as, continue to stir 15min with the speed of 60r/min,
Then the prefabricated additive added, is evacuated to absolute pressure 20mbar, is warming up to 85 DEG C, continues to stir with the speed of 60r/min
50min, is eventually adding remaining polyester polyol PPG2000, under vacuum state, continues to stir 2h with the speed of 50r/min, goes out
Material, detection nco value obtain nano-material modified no-solvent polyurethane woodcare paint to 6.25%.
Comparative example 1：
(1) by 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl
Methane diisocyanate mixes, and 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
It is stand-by to prefabricated additive, it is ensured that to be added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness factor, it is ensured that totally without aqueous vapor, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) by the temperature adjustment of reaction kettle to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
10min is stirred under 60r/min, adds polyether polyol, continues to stir 60min with the speed of 45r/min, obtains polyurethane prepolymer
Body, will first add polyester polyol PE1000 in base polyurethane prepolymer for use as, continue to stir 10min, Ran Houjia with the speed of 45r/min
The prefabricated additive entered, continues to stir 1h, discharging, detection nco value obtains nano material and change to 5.5% with the speed of 50r/min
The no-solvent polyurethane woodcare paint of property.After testing, what prepared by embodiment 1-6 and comparative example is nano-material modified solvent-free poly-
The surface free energy of urethane woodcare paint, hardness, wearability, the result of adhesive force grade and stability are as follows：
As seen from the above table, what the nano-material modified no-solvent polyurethane woodcare paint that prepared by the present invention was 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, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of nano-material modified no-solvent polyurethane woodcare paint, it is characterised 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,
Including 0.001% phosphoric acid, 17% silane coupling agent, 5.6% polybutene, 0.4% Nano carbon white, 4% nanometer titanium dioxide
Titanium, surplus are neopentyl glycol.
A kind of 2. preparation method of nano-material modified no-solvent polyurethane woodcare paint, it is characterised in that：Comprise the following steps：
(1) reaction kettle air-tightness, agitating paddle and kettle wall cleanliness factor are checked, it is ensured that totally without steam and water droplet, Bao Famenguan in kettle
Close, feeding port is opened, and filter installation is correct, stand-by；
(2) temperature adjustment for the reaction kettle for having checked step (1) is to 65 DEG C, and under nitrogen atmosphere, addition is preheated to 40 DEG C
Liquid MDI, 10-15min is stirred under 60-100r/min, adds prefabricated polyether polyol, is continued with the speed of 45-60r/min
10-15min is stirred, obtains base polyurethane prepolymer for use as；
(3) by weight percentage, by 0.001% phosphoric acid, 17% silane coupling agent, 5.6% polybutene, 0.4% nanometer it is white
Carbon black and 4% nano-titanium dioxide are added in neopentyl glycol, and total amount 100%, is uniformly mixed, obtains prefabricated additive, stand-by；
(4) will step (2) prepare base polyurethane prepolymer for use as in first add some polyesters polyalcohol, with the speed of 45-60r/min after
Continuous stirring 10-15min, then adds prefabricated additive prepared by step (3), is evacuated to absolute pressure 20mbar, is warming up to 80-
85 DEG C, continue to stir 50-60min with the speed of 45-60r/min, be eventually adding remaining polyester polyol, under vacuum state, with
The speed of 50-80r/min continues to stir 1-2h, and discharging, obtains nano-material modified no-solvent polyurethane woodcare paint.
3. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the step (2), MDI 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate
With one kind in 2,2 '-methyl diphenylene diisocyanate or its mixture.
4. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the step (2), MDI is replaced by TDI, IPDI, modified MDI, HDI, XDI, PAPI.
5. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the step (2), the molecular weight of prefabricated polyether polyol is 2600-3000.
6. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the step (3), phosphoric acid is that the analysis of 100-300PPM is pure.
7. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the step (3), stand-by timeliness is less than 20min.
8. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the step (4), the mass ratio of some polyesters polyalcohol and remaining polyester polyol is 1:2.5-3.
9. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 2, it is special
Sign is：In the 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, 45-50 parts of polyester polyol, additive 1-5 parts prefabricated, total amount 100
Part, the prefabricated polyether polyol is by adipic acid, terephthalic acid (TPA) and M-phthalic acid and diethylene glycol (DEG) and ethylene glycol hybrid reaction
It is made.
10. a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint according to claim 9, it is special
Sign is：In the step (4), the component of nano-material modified no-solvent polyurethane woodcare paint, by weight, including
39 parts of MDI, 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112375473A (en) * | 2020-10-23 | 2021-02-19 | 上海嘉宝莉涂料有限公司 | Environment-friendly antibacterial water-based paint composition |
| CN112663590A (en) * | 2020-12-22 | 2021-04-16 | 合肥工业大学 | Method for repairing expansive soil slope by modifying and wrapping flexible calcium-based material |
| CN113775062A (en) * | 2021-09-28 | 2021-12-10 | 中铁五局集团第一工程有限责任公司 | Chemical bar planting method in house construction engineering |
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| JPH0978028A (en) * | 1995-09-14 | 1997-03-25 | Yokohama Rubber Co Ltd:The | Solventless primer composition |
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| CN113775062A (en) * | 2021-09-28 | 2021-12-10 | 中铁五局集团第一工程有限责任公司 | Chemical bar planting method in house construction engineering |
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| CN108003774B (en) | 2019-10-11 |
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