CN106279620B - A kind of modified aqueous polyurethane resin and preparation method thereof for woodcare paint - Google Patents
A kind of modified aqueous polyurethane resin and preparation method thereof for woodcare paint Download PDFInfo
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- CN106279620B CN106279620B CN201610643980.6A CN201610643980A CN106279620B CN 106279620 B CN106279620 B CN 106279620B CN 201610643980 A CN201610643980 A CN 201610643980A CN 106279620 B CN106279620 B CN 106279620B
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/44—Polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/61—Polysiloxanes
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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
- C08G18/65—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
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The present invention provides a kind of modified aqueous polyurethane resin and preparation method thereof for woodcare paint, including following raw material components and parts by weight: 35~65 parts of polyalcohol；30~55 parts of polyisocyanates；First 2~6 parts of small molecule chain extender；3~7 parts of anionic hydrophilic chain extender；1~3 part of crosslinking agent；0.1~0.25 part of catalyst；0.5~2.5 part of silane coupling agent；2~5 parts of salt forming agent；Second 2~5 parts of small molecule chain extender；Wherein, polyalcohol includes hydroxy-terminated polysiloxane dihydric alcohol, castor oil and aliphatic polyester binary alcohol, and the weight ratio of hydroxy-terminated polysiloxane dihydric alcohol, castor oil and aliphatic polyester binary alcohol is (2~5): (4~8): (30~50).The dried coating film speed for the modified aqueous polyurethane resin that the present invention obtains is fast, and for glossiness up to 90 ° or more, pencil hardness reaches 1H~2H, water resistance reach with water droplet on film 48 hours it is without exception, surmount national standard.
Description
Technical field
The present invention relates to high molecular polymer fields, specifically disclose a kind of modified aqueous polyurethane tree for woodcare paint
Rouge and preparation method thereof.
Background technique
Woodcare paint is the indispensable component part of wood furniture, can improve the harsh hand that wood furniture has, make house
The tool influence that climate and air humidity do not change.But in current China Furniture Industry, the woodcare paint overwhelming majority or quilt
Solvent wood coatings occupy, and the VOC of discharge has seriously affected the health of people.With mentioning for people's environmental consciousness
Height is increasingly approved by market since aqueous woodware paint has many advantages, such as nontoxic, low pollution, environmental protection.
Currently, water-based acrylic resin research is more, but it haves the defects that hot to stick that cold short, grease resistance is poor hinders
Application of the water-based acrylic resin on woodcare paint.Waterborne polyurethane resin is copolymerized by isocyanates, macromolecular polyol,
Its film be macromolecular polyol soft segment and carbamate hard section assemble respectively arrangement be phase separation structure, the structure is resistance to
With the advantage of day heat in heat, oil resistant and closure, thus waterborne polyurethane resin in terms of the woodcare paint on using not
It is disconnected to be promoted.But that there are hardness is low for the woodcare paint of waterborne polyurethane resin preparation in the prior art, water resistance, glossiness and resistance to
The poor problem of alcohol, causes the product quality of aqueous woodware paint bad.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of modified aqueous polyurethane for woodcare paint is provided
Resin and preparation method thereof, not only mechanical strength is big for the modified aqueous polyurethane resin, and hardness is high, and glossiness is high, also has excellent
Good water-fast, alcohol resistance energy.
In order to realize that object above and other purposes, the present invention are by including that following technical scheme is realized: Yi Zhonggai
Property waterborne polyurethane resin, including following raw material components and parts by weight:
Preferably, the polyalcohol is 45~60 parts.
Preferably, the polyisocyanates is 45~52 parts.
Preferably, first small molecule chain extender is 5~6 parts.
Preferably, the anionic hydrophilic chain extender is 4~5 parts.
Preferably, the crosslinking agent is 3 parts.
Preferably, the catalyst is 0.15~0.20 part of
Preferably, the silane coupling agent is 1~2 part.
Preferably, the salt forming agent is 4~5 parts.
Preferably, second small molecule chain extender is 2~3 parts.
Wherein, the polyalcohol includes hydroxy-terminated polysiloxane dihydric alcohol, castor oil and aliphatic polyester binary alcohol, described
The weight ratio of hydroxy-terminated polysiloxane dihydric alcohol, the castor oil and the aliphatic polyester binary alcohol is (2~5): (4~
8): (30~50), the aliphatic polyester binary alcohol be selected from one of polycarbonate glycol and polycaprolactone diols or
Two kinds of person.
Preferably, the structural formula of the hydroxy-terminated polysiloxane dihydric alcohol is as follows:
In structural formula, R1And R2It is CH3、CH2CH3Or CH2CH2CH3, n be 1~1000 integer.
Preferably, the number-average molecular weight of the hydroxy-terminated polysiloxane dihydric alcohol is 1000,2000,3000, more preferably
2000。
Preferably, the number-average molecular weight of the castor oil is 1000,2000,3000, more preferably 2000.
Preferably, the number-average molecular weight of the polycarbonate glycol is 1000,2000, more preferably 1000.
Preferably, the number-average molecular weight of the polycaprolactone diols is 1000,2000, more preferably 1000.
Preferably, the diisocyanate is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone
Any one in diisocyanate, hexamethylene diisocyanate and dicyclohexyl diisocyanate is a variety of.
Preferably, first small molecule chain extender is ethylene glycol, 1,4-butanediol, 2- methyl-1,3-propanediol, Isosorbide-5-Nitrae-
Any one or more in cyclohexanedimethanol.
Preferably, second small molecule chain extender is in ethylenediamine, Isosorbide-5-Nitrae-hexamethylene dimethylamine, isophorone diamine
It is one or more.
Preferably, the anionic hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid.
Preferably, the crosslinking agent is trimethylolpropane.
Preferably, the catalyst be selected from organic zinc compound, organo-tin compound, organic alkali metal salt, tertiary amine and its
Any one in salt compound or two kinds.
It is highly preferred that the organic zinc compound in zinc Isoocatanoate, zinc octoate and zinc acetylacetonate any one；Institute
State organo-tin compound in dibutyl tin laurate and stannous octoate any one；The organic alkali metal salt is acetic acid
Sodium.
Preferably, the silane coupling agent includes γ-glycidyl ether oxygen propyl trimethoxy silicane, structural formula are as follows:
A kind of method that the present invention discloses waterborne polyurethane resin for preparing modification as described above, including following step
Rapid: ratio mixes the hydroxyl polysiloxane dihydric alcohol, the castor oil and the aliphatic polyester binary alcohol by weight
It closes, the diisocyanate is then added, be warming up to 80~90 DEG C, 2~3h is kept the temperature, after being cooled to 40~50 DEG C, described in addition
Anionic hydrophilic chain extender, first small molecule chain extender and the crosslinking agent, add the catalyst, are warming up to 70
~80 DEG C, 2~4h is kept the temperature, the first performed polymer is obtained；After first performed polymer is cooled to 40~50 DEG C, the silane is added
Coupling agent keeps the temperature 5~20min, obtains the second performed polymer；Second performed polymer is cooled to 10~20 DEG C, institute is then added
It states salt forming agent to be neutralized, second small molecule chain extender is added after ice water is added, be evaporated under reduced pressure, obtain the poly- ammonia of modified water-soluble
Ester resin.
Preferably, the anionic hydrophilic chain extender, first small molecule chain extender and the crosslinking agent is added
Being added solvent for adjusting solution concentration simultaneously, the solvent is acetone, butanone, methyl ethyl ketone, N-Methyl pyrrolidone and N,
One of dinethylformamide is a variety of.
The effect of the solvent is to adjust the viscosity of reaction solution.The additive amount of the solvent can need to take the circumstances into consideration according to reaction
Addition.The solvent is distilled removing in the vacuum distillation stage.
The modified water-soluble that the present invention discloses modified aqueous polyurethane resin or method described above preparation described above is poly-
Purposes of the urethane resin in woodcare paint.
Preferably, the purposes obtains wood by the modified aqueous polyurethane resin after thickening, wetting, defoaming treatment
Device paint.
It is described above thickening, wetting, defoaming treatment step be all made of in the prior art usual way progress.
The present invention selects the primary raw material of polycarbonate glycol and polycaprolactone diols as macromolecular polyol, together
When a small amount of hydroxy-terminated polysiloxane dihydric alcohol is added, since the hydroxyl of the macromolecule dihydric alcohol is located in siloxane chain, when connecing
When entering in polyurethane backbone, siloxanes is easy to make material have preferable surface property to surface migration, can improve siloxanes
Mechanical performance, and material surface energy is greatly reduced under the premise of not reducing the mechanical property of materials, so that the water resistance of material
It greatly improves.Meanwhile the castor oil polyhydric alcohol of a small amount of three-functionality-degree is added, since there is castor oil long-chain fat base can be improved
The water resistance of polyurethane, while castor oil hydroxyl containing there are three, can be improved the degree of cross linking of polyurethane system, to the comprehensive of polyurethane
Closing performance has larger improvement, so that the modified aqueous polyurethane resin good combination property obtained, modified aqueous polyurethane resin is not
Only mechanical strength is big, and hardness is high, and glossiness is high, also has excellent water resistance energy.
Silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane is added in the present invention in the synthesis process simultaneously,
The silane coupling agent is containing there are three the silane of silicon oxygen bond and epoxy-functional, due to the hydrolysis of silicon oxygen bond, in polyurethane system
Middle formation cross-linked network structure, is remarkably improved mechanical strength, the hardness of film, and siloxanes can be into the surface enrichment of material
One step improves the water resistance of material, while the presence of epoxy-functional can significantly improve the adhesive property of material.
In conclusion the present invention provides a kind of modified aqueous polyurethane resin and preparation method thereof for woodcare paint,
It has the beneficial effect that
The modified aqueous polyurethane resin lotion that the present invention obtains is transparent, and stability is good, and period of storage is long, and modified water-soluble is poly-
Not only rate of drying is fast, hardness is high, glossiness is high for the film of urethane resin, adhesive force is high, but also resistance to alcohol, chemical resistance are excellent
Different, water resistance is splendid.
The dried coating film speed for the modified aqueous polyurethane resin that the present invention obtains is fast, and glossiness is up to 90 ° or more, pencil
Hardness reaches H~2H, water resistance reach with water droplet on film 48 hours it is without exception, much surmount national standard；Alcohol resistance is reachable
To by mass fraction be 50% ethanol solution drip on film 2 hours it is without exception.
Stable preparation process of the present invention reacts easily controllable, and the present invention uses biomass material castor oil part generation
Waterborne polyurethane resin is synthesized for oil polyalcohol, the utilization rate of resource not only can be improved, and can be aqueous polyurethane work
Industry provides cheap raw material sources, reduces the dependence to oil product.Cost can be reduced simultaneously, to aqueous polyurethane industrial
Development have important strategic importance.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.It should be understood that embodiment is merely to illustrate the present invention, rather than limit
The scope of the present invention.
Embodiment 1
30g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, 2g terminal hydroxy group are added into three-necked flask
Then polysiloxane binary alcohol is added 50g isophorone diisocyanate and is warming up to 85 DEG C, reacts 2h, be cooled to 50 DEG C, be added
6g dihydromethyl propionic acid, 3g trimethylolpropane, 4g1,4- butanediol, 0.2g stannous octoate and acetone, after stirring, are heated to 80
DEG C, 3h is reacted, is cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl trimethoxy silicane is added, 10min is reacted, is cooled to 10
DEG C, 4.5g triethylamine is added and neutralizes, 230g ice water emulsion dispersion is added, adds chain extension after 2.8g ethylenediamine, continues emulsification point
It dissipates, acetone is then removed by vacuum distillation, obtain modified aqueous polyurethane resin lotion.
Embodiment 2
30g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, the end 3.5g hydroxyl are added into three-necked flask
Then based polysiloxane dihydric alcohol is added 50g isophorone diisocyanate and is warming up to 85 DEG C, reacts 2h, be cooled to 40 DEG C, add
Enter 6g dihydromethyl propionic acid, 3g trimethylolpropane, 4g1,4- butanediol, 0.2g stannous octoate and acetone, after stirring, is heated to
75 DEG C, 4h is reacted, is cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl trimethoxy silicane is added, 10min is reacted, is cooled to
15 DEG C, 4.5g triethylamine is added and neutralizes, 230g ice water emulsion dispersion is added, while chain extension after 2.8g ethylenediamine is added, continues cream
Change dispersion, acetone is then removed by vacuum distillation, obtains modified aqueous polyurethane resin lotion.
Embodiment 3
30g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, 2g terminal hydroxy group are added into three-necked flask
Then polysiloxane binary alcohol is added 50g isophorone diisocyanate and is warming up to 90 DEG C, reacts 2h, be cooled to 45 DEG C, be added
6g dihydromethyl propionic acid, 3g trimethylolpropane, 4g1,4- butanediol, 0.2g stannous octoate and acetone, after stirring, are heated to 80
DEG C, 3h is reacted, is cooled to 40 DEG C, 2g γ-glycidyl ether oxygen propyl trimethoxy silicane is added, 15min is reacted, is cooled to 15
DEG C, 4.5g triethylamine is added and neutralizes, 230g ice water emulsion dispersion is added, while chain extension after 2.8g ethylenediamine is added, continues to emulsify
Then dispersion removes acetone by vacuum distillation, obtain modified aqueous polyurethane resin lotion.
Embodiment 4
30g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, 2g terminal hydroxy group are added into three-necked flask
Then polysiloxane binary alcohol is added 30g isophorone diisocyanate and 25g dicyclohexyl diisocyanate, is warming up to 85
DEG C, 2h is reacted, is cooled to 40 DEG C, 6g dihydromethyl propionic acid, 3g trimethylolpropane, 4g1,4- butanediol, 0.2g octanoic acid is added
Stannous and acetone after stirring, are heated to 75 DEG C, react 4h, be cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl front three is added
Oxysilane reacts 10min, is cooled to 15 DEG C, and 4.5g triethylamine is added and neutralizes, 230g ice water emulsion dispersion is added, adds simultaneously
Enter chain extension after 2.8g ethylenediamine, continue emulsion dispersion, acetone is then removed by vacuum distillation, obtains modified aqueous polyurethane tree
Fat liquor.
Embodiment 5
30g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, 2g terminal hydroxy group are added into three-necked flask
Then polysiloxane binary alcohol is added 30g isophorone diisocyanate and 25g dicyclohexyl diisocyanate, is warming up to 80
DEG C, 3h is reacted, is cooled to 50 DEG C, 6g dihydromethyl propionic acid, 3g trimethylolpropane, 4g1,4- butanediol, 0.2g octanoic acid is added
Stannous and acetone after stirring, are heated to 80 DEG C, react 3h, be cooled to 40 DEG C, 2g γ-glycidyl ether oxygen propyl front three is added
Oxysilane reacts 10min, is cooled to 15 DEG C, and 4.5g triethylamine is added and neutralizes, 230g ice water emulsion dispersion is added, adds simultaneously
Enter chain extension after 2.8g ethylenediamine, continue emulsion dispersion, acetone is then removed by vacuum distillation, obtains modified aqueous polyurethane tree
Fat liquor.
Performance detection:
The performance for the modified aqueous polyurethane resin lotion that embodiment 1 to 5 obtains, including emulsion appearance, solid content are detected,
The modified aqueous polyurethane emulsion that embodiment 1 to 5 is obtained carries out film, and GB/T 23999-2009 is " indoor according to national standards
Decorations water-borne wood coating " evaluation film lustrous surface, water resistance, alcohol resistance and pencil hardness, according to country mark
Quasi- GB1743-79 carries out glossiness test, carries out adhesive force test according to standard GB/T/T9286-1998, marks according to country
Quasi- GB/T1733-1993 carries out water resistance test, carries out pencil hardness test according to standard GB/T/T6739-1996.Detection
The results are shown in Table 1.
The results of property for the modified aqueous polyurethane resin lotion that 1 embodiment 1 to 5 of table obtains
As seen from Table 1, embodiment 1 to 5 obtain modified aqueous polyurethane resin lotion solid content be 34~
36wt%, the glossiness of film are 90~92 °；The drying time for the modified aqueous polyurethane resin that embodiment 1 to 5 obtains is significantly
Lower than national standard, drying time is saved；Li≤1 Tu film Fu for the modified aqueous polyurethane resin that embodiment 1 to 5 obtains
Grade, adhesive force are stronger；By tap water drop to embodiment 1 to 5 obtain modified aqueous polyurethane film on 48 hours it is without exception,
Illustrate that water-resistance property of coating is good；By the ethanol solution that mass fraction is 50% drop on film 2 hours it is without exception, illustrate the resistance to of film
Alcohol is excellent；And the hardness of film for the modified aqueous polyurethane that embodiment 1 to 5 obtains reaches 1H~2H, and hardness of film is strong.Institute
With embodiment 1 to 5 obtains property of the waterborne polyurethane resin in terms of hardness, alcohol resistance, water resistance and glossiness and adhesive force
Can be excellent, much surmount national standard.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention
It is interior.
Claims (8)
1. a kind of modified aqueous polyurethane resin, it is characterised in that: be made of following raw material components and parts by weight:
Wherein, the polyalcohol includes hydroxy-terminated polysiloxane dihydric alcohol, castor oil and aliphatic polyester binary alcohol, the end hydroxyl
The weight ratio of based polysiloxane dihydric alcohol, the castor oil and the aliphatic polyester binary alcohol is (2~5): (4~8):
(30~50)；The aliphatic polyester binary alcohol is selected from one of polycarbonate glycol and polycaprolactone diols or two
Kind；The silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, structural formula are as follows:
The crosslinking agent is trimethylolpropane；
The structural formula of the hydroxy-terminated polysiloxane dihydric alcohol are as follows:
In structural formula, R1And R2It is CH3、CH2CH3Or CH2CH2CH3, n be 1~1000 integer.
2. modified aqueous polyurethane resin as described in claim 1, it is characterised in that: it is different that the diisocyanate is selected from toluene two
Cyanate, methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl two
Any one in isocyanates is a variety of.
3. modified aqueous polyurethane resin as described in claim 1, it is characterised in that: first small molecule chain extender is second two
Alcohol, 1,4- butanediol, 2- methyl-1,3-propanediol, any one or more in 1,4 cyclohexane dimethanol；
And/or second small molecule chain extender is selected from ethylenediamine, Isosorbide-5-Nitrae-hexamethylene dimethylamine, one of isophorone diamine
Or it is a variety of.
4. modified aqueous polyurethane resin as described in claim 1, it is characterised in that: the anionic hydrophilic chain extender is two
Hydroxymethyl propionic acid or dimethylolpropionic acid.
5. modified aqueous polyurethane resin as described in claim 1, it is characterised in that: the catalyst is selected from organic zinc chemical combination
Any one in object, organo-tin compound, organic alkali metal salt, tertiary amine and its salt compound or two kinds.
6. a kind of method for preparing the modified aqueous polyurethane resin as described in claim 1 to 5 is any, it is characterised in that: including
Following steps:
Ratio mixes the hydroxyl polysiloxane dihydric alcohol, the castor oil and the aliphatic polyester binary alcohol by weight
It closes, the diisocyanate is then added, be warming up to 80~90 DEG C, 2~3h is kept the temperature, after being cooled to 40~50 DEG C, described in addition
Anionic hydrophilic chain extender, first small molecule chain extender and the crosslinking agent, add the catalyst, are warming up to 70
~80 DEG C, 2~4h is kept the temperature, the first performed polymer is obtained；
After first performed polymer is cooled to 40~50 DEG C, the silane coupling agent is added, keeps the temperature 5~20min, obtains second
Performed polymer；
Second performed polymer is cooled to 10~20 DEG C, the salt forming agent is then added and is neutralized, is added after ice water is added
Second small molecule chain extender, vacuum distillation obtain modified aqueous polyurethane resin.
7. the method for modified aqueous polyurethane resin as claimed in claim 6, it is characterised in that: the anionic parent is added
The solvent for adjusting solution concentration, institute are added while water chain extender, first small molecule chain extender and the crosslinking agent
Stating solvent is one of acetone, butanone, methyl ethyl ketone, N-Methyl pyrrolidone and N,N-dimethylformamide or a variety of.
8. modified aqueous polyurethane resin as claimed in claim 1 to 5 or method according to claim 6 or 7
Purposes of the modified aqueous polyurethane resin of acquisition in woodcare paint.
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| CN107141434B (en) * | 2017-06-08 | 2019-12-27 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof |
| CN107602814A (en) * | 2017-08-21 | 2018-01-19 | 合肥科天水性科技有限责任公司 | A kind of cationic water polyurethane resin for spinning coating and preparation method thereof |
| CN108276551A (en) * | 2017-12-26 | 2018-07-13 | 合肥科天水性科技有限责任公司 | A kind of multiple cross-linked modified aqueous polyurethane resin of biology base and its preparation method and application |
| CN108948314A (en) * | 2018-05-23 | 2018-12-07 | 安徽省高雅家居有限公司 | A kind of waterborne polyurethane resin and preparation method thereof for woodcarving surface treatment |
| CN109824850A (en) * | 2019-03-06 | 2019-05-31 | 广东工业大学 | A kind of dual-component aqueous polyurethane and its preparation method and application |
| CN111187392A (en) * | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Preparation of alcohol scrubbing resistant and acid and alkali resistant waterborne polyurethane |
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| CN111662633B (en) * | 2020-06-24 | 2021-11-30 | 广东达尔新型材料有限公司 | Anti-static wear-resistant polyurethane floor coating and preparation method thereof |
| CN113025184A (en) * | 2021-02-08 | 2021-06-25 | 合肥科天水性科技有限责任公司 | High-adhesion waterborne polyurethane coating resin and preparation method thereof |
| CN116396455B (en) * | 2023-05-26 | 2023-08-11 | 广州艾科新材料股份有限公司 | Method for preparing polyol and polyurethane from reclaimed oil |
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