CN109486403A - A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent - Google Patents
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent Download PDFInfo
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- CN109486403A CN109486403A CN201811394224.XA CN201811394224A CN109486403A CN 109486403 A CN109486403 A CN 109486403A CN 201811394224 A CN201811394224 A CN 201811394224A CN 109486403 A CN109486403 A CN 109486403A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses the preparation methods of a kind of waterproof aqueous polyurethane coating and finishing agent, dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 75 ~ 80 DEG C of 1 ~ 2h of reaction, triethylamine 8.9g is added and carries out 30 ~ 60min of neutralization reaction, water 130g is added to carry out 1 ~ 2h of emulsification, and it is added 2,6- lutidines -4- carboxylate methyl ester 0.6g, 85 DEG C of reaction temperature, reaction time 1h, regulation system pH is 7 ~ 8, obtains aqueous polyurethane coating；In the template that obtained mixed solution and obtained aqueous polyurethane coating are poured on, with wavelength be 260nm ultraviolet light template on mixed solution 20min, obtain the superoleophobic underwater self-cleaning composite membrane of polymer of the biomimetic features of high mechanical strength, as waterproof aqueous polyurethane coating and finishing agent, gained film have good waterproof performance.
Description
Technical field
The invention belongs to aqueous polyurethane coating fields, and in particular to a kind of waterproof aqueous polyurethane coating and finishing agent
Preparation method.
Background technique
Aqueous polyurethane is to replace organic solvent as the new polyurethane system of decentralized medium using water, and also referred to as water dispersion is poly-
Urethane, aqueous polyurethane or water-based polyurethane.Aqueous polyurethane takes water as a solvent, pollution-free, safe and reliable, mechanical performance is excellent
Good, the advantages that compatibility is good, easily modified.
The Water-borne modification of polyurethane resin gradually replaces solvent type, becomes the important directions of polyurethane industrial development.It is aqueous
Polyurethane can be widely applied to coating, adhesive, fabric coating and finishing agent, leather finishing agent, sheet surface treating agent and fibre
Tie up surface treating agent.
According to the charge property of hydrophilic radical, aqueous polyurethane can be divided into anion-type water-thinned polyurethane, cationic water
Property polyurethane and non-ion aqueous polyurethane.Wherein anionic is mostly important, is divided into carboxylic acid type and sulfonic acid type two major classes.
Polyether-type, polyester-type and polyethers, polyester mixed type can be divided into according to synthon difference aqueous polyurethane.According to selection
Diisocyanate difference, aqueous polyurethane can be divided into aromatic series and aliphatic again, or be specifically divided into TDI type, HDI type etc.
Deng.
Monocomponent waterborne polyurethane and dual-component aqueous polyurethane can be divided into according to product packaging form aqueous polyurethane.
The entire synthesis process of aqueous polyurethane can be divided into two stages.First stage is gradually to polymerize in advance, i.e., by oligomer
Glycol, chain extender, aqueous monomers, diisocyanate gradually polymerize the water for generating that relative molecular mass is l000 magnitude by solution
Property base polyurethane prepolymer for use as；Second stage is the dispersion of performed polymer in water after neutralizing.
Fish scale is combined between layers relatively closely, single scale shows irregular centre in folded layered distribution
6 thin side shape shapes of thick both sides, due to its unique arrangement mode, there are exposed region and non-exposed region in fish scale surface, by upper one layer
Being covered is non-exposed region, and fish scale surface is divided into 3 areas, is embedded in skin corium and is covered and is
Push up area；Being exposed to outer is base area;Two sides are lateral areas, and the focus in 3rd area is that squama is burnt.Observed under electron microscope scale table
The part that there are concentric circles in face is that ringed line is referred to as squama ridge and discontinuous radioactive ray part i.e. squama ditch, and most of fish scale has 3
Squama ditch,
The shrinkage pool on fish scale surface is copied, three-dimensional fish scale shape shrinkage pool simplified model is established, which has more apparent drag reduction effect
Fruit, relative to smooth surface, fish scale shape pit surface improves the waterproofness of material using the super hydrophobic surface of imitative fish scale.
201610553980.7 disclosing a kind of preparation method of environment-friendly type polyurethane waterproofing paint, including by hexylene glycol
Obtain crystalline polyester polyols after specifically being reacted with 6 ~ 12 alkyl dicarboxylic aids, then by crystalline polyester polyols 5 ~
10 parts and 10 ~ 20 parts of polyurethane resin, 1 ~ 5 part of '-diphenylmethane diisocyanate, 10 ~ 20 parts of chlorinated paraffin, polyether polyol 5
~ 15 parts, 10 ~ 20 parts of light calcium, 10 ~ 20 parts of coarse whiting, 0.5 ~ 2 part of aromatic naphtha, 0.05 ~ 0.1 part of catalyst carry out being mixed to get ring
Protect type polyurethane water-repellent paint.Highly toxic TDI is not used in the present invention, environmentally protective, obtained polyurethane water-proof paint surface drying
Time is not more than 7h, does solid work the time no more than 22h, and adhesion strength is more than 1 .1Mpa, and elongation at break is more than 580%, tearing
Intensity is more than 25N/mm, and advantage of the invention is to carry out waterproof using aromatic naphtha, the waterproof of polyurethane is big at present without using TDI
Majority carries out waterproof using waterproof material.
Summary of the invention
The invention discloses the preparation methods of a kind of waterproof aqueous polyurethane coating and finishing agent, use polyurethane coating
With maleic anhydride, nano-titanium dioxide, p-methyl benzenesulfonic acid action of ultraviolet radiation again under, improve the anti-of polyurethane coating and finishing agent
Aqueous ability, while the surface drying of polyurethane is improved using 2,6- lutidines -4- carboxylate methyl ester and is done solid work the time, dimethyl benzene
Amine and six molybdic acids improve its waterproof performance, and the solidification and crosslinking that polyurethane is improved using curing agent and cure boosters are combined,
Improve its waterproof performance.
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by dihydric alcohol 18.4g, isocyanates
57.6g mixing under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g, 1 ~ 3h is reacted at 70 ~ 80 DEG C, is obtained
Base polyurethane prepolymer for use as A；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 75 ~ 80 DEG C of 1 ~ 2h of reaction, triethylamine is added
8.9g carries out 30 ~ 60min of neutralization reaction, adds water 130g to carry out 1 ~ 2h of emulsification, and 2,6- lutidines -4- carboxylate methyl ester is added
0.6g, 85 DEG C of reaction temperature, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) it is 6: 1: 0.1 according to mass ratio by dimethyl silicone polymer, curing agent, cure boosters and the chloro- n-butyl alcohol of 4-:
0.01 ratio is mixed to get mixture (total weight 12g), then falls mixture and has fish scale one in what step 3) obtained
On the fish-skin in face, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 120 DEG C and solidifies 1 ~ 2 h；It, will after solidification
Mixture and the fish-skin removing of dimethyl silicone polymer, curing agent, cure boosters and the chloro- n-butyl alcohol of 4-, obtain replica fish scale
Surface have fish scale antistructure cured dimethyl silicone polymer and curing agent mixture template；
5) by maleic anhydride 12g, 1 ~ 3g of nano-titanium dioxide, 1 ~ 3g of p-methyl benzenesulfonic acid, dimethylaniline 3.1g, six molybdic acids
1.7g, tetrabutylammonium bromide 0.3g, which are dissolved in 40 ~ 50g of water, obtains mixed solution, by ultrasound 15 minutes, stirs 2 ~ 3h, makes to mix
Solution is closed to be uniformly mixed；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on what step 4) obtained
In template, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-silica
Change titanium crosslinks polymerization under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are shelled
From, and repeated flushing into the water, unreacted maleic anhydride monomer is removed, the super thin of the biomimetic features of high mechanical strength is obtained
The underwater self-cleaning composite membrane of polymer of oil, as waterproof aqueous polyurethane coating and finishing agent.
The dihydric alcohol is any one of polytetrahydrofuran ether glycol, polycarbonate glycol, 1,4- butanediol；
The isocyanates is '-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate
Any one；
The curing agent be poly(N-isopropylacrylamide), p-chlorotrichlormethyl, N, N- diethyl hydroxylamine any one；
The cure boosters are 3- nitro -4- aminoanisole, 2- nitro -4- aminoanisole, bis- (the benzene sulphurs of 4,4'- oxo
Acyl chlorides), 2,4- dimethylacetamide antifebrin any one.
Present invention has an advantage that
(1) shrinkage pool for copying fish scale surface, establishes three-dimensional fish scale shape shrinkage pool simplified model, which has more apparent waterproof
Performance.
(2) 2,6- lutidines -4- carboxylate methyl ester improves the surface drying of polyurethane and does solid work the time.
(3) dimethylaniline and six molybdic acids improve its waterproof performance, and poly- ammonia is improved using curing agent and cure boosters
The solidification and crosslinking of ester combine, and improve its waterproof performance, and tetrabutylammonium bromide enhances film low temperature folding resistance, and the chloro- n-butyl alcohol of 4- is just
It is removed in curing agent and fish scale.
Specific embodiment
Embodiment 1
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by polytetrahydrofuran ether glycol 18.4g, two
Phenylmethane diisocyanate 57.6g mixing, under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g, at 70 DEG C
1h is reacted, base polyurethane prepolymer for use as A is obtained；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 75 DEG C of reaction 1h, triethylamine 8.9g is added and carries out
Neutralization reaction 30min adds water 130g to carry out emulsification 1h, and 2,6- lutidines -4- carboxylate methyl ester 0.6g, reaction temperature is added
85 DEG C, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) by dimethyl silicone polymer, poly(N-isopropylacrylamide) curing agent, 3- nitro -4- methoxybenzene amine curing
Synergist and the chloro- n-butyl alcohol of 4- are mixed to get mixture (total weight according to the ratio that mass ratio is 6: 1: 0.1:0.01
12g), then mixture is fallen on the fish-skin with fish scale one side that step 3) obtains, after vacuumizing in vacuum tank
It is transferred in the baking oven that temperature is 120 DEG C and solidifies 1 h；After solidification, by dimethyl silicone polymer, poly- (N- isopropyl acrylamide
Amine) curing agent, the mixture of 3- nitro -4- aminoanisole cure boosters and the chloro- n-butyl alcohol of 4- and fish-skin removing, it is answered
The surface of type fish scale has the cured dimethyl silicone polymer of fish scale antistructure and the mixing of poly(N-isopropylacrylamide)
Object template；
5) by maleic anhydride 12g, nano-titanium dioxide 1g, p-methyl benzenesulfonic acid 1g, dimethylaniline 3.1g, six molybdic acid 1.7g, four
Butylammonium bromide 0.3g, which is dissolved in water 40g, obtains mixed solution, by ultrasound 15 minutes, stirs 2h, keeps mixed solution mixing equal
It is even；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on what step 4) obtained
In template, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-silica
Change titanium crosslinks polymerization under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are shelled
From, and repeated flushing into the water, unreacted maleic anhydride monomer is removed, the super thin of the biomimetic features of high mechanical strength is obtained
The underwater self-cleaning composite membrane of polymer of oil, as waterproof aqueous polyurethane coating and finishing agent.
Embodiment 2
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by polycarbonate glycol 18.4g, different Fo Er
Ketone diisocyanate 57.6g mixing is reacted at 80 DEG C under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g
3h obtains base polyurethane prepolymer for use as A；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 80 DEG C of reaction 2h, triethylamine 8.9g is added and carries out
Neutralization reaction 60min adds water 130g to carry out emulsification 2h, and 2,6- lutidines -4- carboxylate methyl ester 0.6g, reaction temperature is added
85 DEG C, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) it is according to mass ratio by dimethyl silicone polymer, p-chlorotrichlormethyl curing agent, cure boosters and the chloro- n-butyl alcohol of 4-
6: 1: 0.1:0.01 ratio is mixed to get mixture (total weight 12g), then obtains mixture in step 3)
On fish-skin with fish scale one side, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 120 DEG C and solidifies 2 h；Gu
After change, by dimethyl silicone polymer, p-chlorotrichlormethyl curing agent, 2- nitro -4- aminoanisole cure boosters and 4-
The mixture and fish-skin of chloro- n-butyl alcohol are removed, and the surface for obtaining replica fish scale has the cured poly dimethyl of fish scale antistructure
The mixture template of siloxanes and p-chlorotrichlormethyl curing agent；
5) by maleic anhydride 12g, nano-titanium dioxide 3g, p-methyl benzenesulfonic acid 3g, dimethylaniline 3.1g, six molybdic acid 1.7g, four
Butylammonium bromide 0.3g, which is dissolved in water 50g, obtains mixed solution, by ultrasonic 15min, stirs 3h, keeps mixed solution mixing equal
It is even；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on what step 4) obtained
In template, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-silica
Change titanium crosslinks polymerization under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are shelled
From, and repeated flushing into the water, unreacted maleic anhydride monomer is removed, the super thin of the biomimetic features of high mechanical strength is obtained
The underwater self-cleaning composite membrane of polymer of oil, as waterproof aqueous polyurethane coating and finishing agent.
Embodiment 3
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by 1,4-butanediol 18.4g, hexa-methylene
Diisocyanate 57.6g mixing reacts 2h at 75 DEG C under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g,
Obtain base polyurethane prepolymer for use as A；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 78 DEG C of reaction 1.5h, addition triethylamine 8.9g into
Row neutralization reaction 45min adds water 130g to carry out emulsification 1.5h, and 2,6- lutidines -4- carboxylate methyl ester 0.6g is added, reaction
85 DEG C of temperature, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) by dimethyl silicone polymer, N, bis- (benzene sulfonyl chloride) cure boosters of N- diethyl hydroxylamine curing agent, 4,4'- oxo and
The chloro- n-butyl alcohol of 4- is mixed to get mixture (total weight 12g) according to the ratio that mass ratio is 6: 1: 0.1:0.01, then will
Mixture falls on the fish-skin with fish scale one side that step 3) obtains, and being transferred to temperature after vacuumizing in vacuum tank is
Solidify 1.5h in 120 DEG C of baking oven；After solidification, by dimethyl silicone polymer, curing agent, cure boosters and the chloro- 1- fourth of 4-
The mixture of alcohol and fish-skin are removed, obtain replica fish scale surface have the cured dimethyl silicone polymer of fish scale antistructure with
The mixture template of curing agent；
5) by maleic anhydride 12g, nano-titanium dioxide 2g, p-methyl benzenesulfonic acid 2g, dimethylaniline 3.1g, six molybdic acid 1.7g, four
Butylammonium bromide 0.3g, which is dissolved in water 45g, obtains mixed solution, by ultrasound 15 minutes, stirs 2.5h, mixes mixed solution
Uniformly；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on what step 4) obtained
In template, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-silica
Change titanium crosslinks polymerization under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are shelled
From, and repeated flushing into the water, unreacted maleic anhydride monomer is removed, the super thin of the biomimetic features of high mechanical strength is obtained
The underwater self-cleaning composite membrane of polymer of oil, as waterproof aqueous polyurethane coating and finishing agent.
Embodiment 4
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by polycarbonate glycol 18.4g, hexichol first
Alkane diisocyanate 57.6g mixing is reacted at 80 DEG C under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g
1h obtains base polyurethane prepolymer for use as A；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 75 DEG C of reaction 2h, triethylamine 8.9g is added and carries out
Neutralization reaction 60min adds water 130g to carry out emulsification 1h, and 2,6- lutidines -4- carboxylate methyl ester 0.6g, reaction temperature is added
85 DEG C, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) dimethyl silicone polymer, poly(N-isopropylacrylamide) curing agent, 2,4- dimethylacetamide antifebrin are solidified
Synergist and the chloro- n-butyl alcohol of 4- are mixed to get mixture (total weight according to the ratio that mass ratio is 6: 1: 0.1:0.01
12g), then mixture is fallen on the fish-skin with fish scale one side that step 3) obtains, after vacuumizing in vacuum tank
It is transferred in the baking oven that temperature is 120 DEG C and solidifies 1 h；After solidification, by dimethyl silicone polymer, curing agent, cure boosters
It is removed with the mixture and fish-skin of the chloro- n-butyl alcohol of 4-, the surface for obtaining replica fish scale has cured poly- the two of fish scale antistructure
The mixture template of methylsiloxane and curing agent；
5) by maleic anhydride 12g, nano-titanium dioxide 1g, p-methyl benzenesulfonic acid 3g, dimethylaniline 3.1g, six molybdic acid 1.7g, four
Butylammonium bromide 0.3g, which is dissolved in water 50g, obtains mixed solution, by ultrasound 15 minutes, stirs 2h, keeps mixed solution mixing equal
It is even；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on the template that step 4) obtains
On, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-titanium dioxide
Polymerization is crosslinked under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are removed, and
Repeated flushing into the water removes unreacted maleic anhydride monomer, obtains the superoleophobic of the biomimetic features of high mechanical strength
Underwater self-cleaning composite membrane of polymer, as waterproof aqueous polyurethane coating and finishing agent.
Embodiment 5
A kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by 1,4-butanediol 18.4g, diphenyl-methane
Diisocyanate 57.6g mixing reacts 3h at 70 DEG C under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g,
Obtain base polyurethane prepolymer for use as A；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 80 DEG C of reaction 2h, triethylamine 8.9g is added and carries out
Neutralization reaction 30min adds water 130g to carry out emulsification 1h, and 2,6- lutidines -4- carboxylate methyl ester 0.6g, reaction temperature is added
85 DEG C, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) by dimethyl silicone polymer, p-chlorotrichlormethyl curing agent, 3- nitro -4- methoxybenzene amine curing
Synergist and the chloro- n-butyl alcohol of 4- are mixed to get mixture (total weight according to the ratio that mass ratio is 6: 1: 0.1:0.01
12g), then mixture is fallen on the fish-skin with fish scale one side that step 3) obtains, after vacuumizing in vacuum tank
It is transferred in the baking oven that temperature is 120 DEG C and solidifies 2 h；After solidification, by dimethyl silicone polymer, curing agent, cure boosters and
The mixture and fish-skin of the chloro- n-butyl alcohol of 4- are removed, and the surface for obtaining replica fish scale has the cured poly- diformazan of fish scale antistructure
The mixture template of radical siloxane and curing agent；
5) by maleic anhydride 12g, nano-titanium dioxide 1.2g, p-methyl benzenesulfonic acid 1.6g, dimethylaniline 3.1g, six molybdic acids
1.7g, tetrabutylammonium bromide 0.3g, which are dissolved in water 45g, obtains mixed solution, by ultrasound 15 minutes, stirs 2.5h, makes to mix molten
Liquid is uniformly mixed；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on what step 4) obtained
In template, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-silica
Change titanium crosslinks polymerization under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are shelled
From, and repeated flushing into the water, unreacted maleic anhydride monomer is removed, the super thin of the biomimetic features of high mechanical strength is obtained
The underwater self-cleaning composite membrane of polymer of oil, as waterproof aqueous polyurethane coating and finishing agent.
Performance test: as can be seen that with reference to GB/T 19250-2013 " polyurethane water-proof paint ", film outward appearance is impregnated
Two synthesis measurings of (96h), impermeability, wherein film outward appearance, which impregnates to use, takes appropriate lotion to be evenly applied on glass plate, and one
Determine that glass plate is put into deionized water after drying and forming-film at temperature and impregnate, observation film becomes blue, whitens, blisters, sends out wrinkle, is de-
The case where falling.
1 test data of table
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative sample 1 | Comparative sample 2 | |
| It stretches strong Degree/mpa | 6.56 | 6.34 | 6.78 | 6.89 | 6.48 | 4.58 | 6.52 |
| Extension at break Rate/% | 482 | 488 | 465 | 475 | 464 | 586 | 153 |
| Tearing strength | 36 | 42 | 48 | 47 | 53 | 32 | 12 |
| Low-temperature bending Property/DEG C≤ | - 35, nothing is split Line | - 35, nothing is split Line | - 35, nothing is split Line | - 35, nothing is split Line | - 35, nothing is split Line | - 35, nothing is split Line | - 35, have Crackle |
| Impermeability | 0.3MPa, 120min, no It is permeable | 0.3MPa, 120min, no It is permeable | 0.3MPa, 120min, no It is permeable | 0.3MPa, 120min, no It is permeable | 0.3MPa, 120min, no It is permeable | 0.3MPa, 120min, portion Divide permeable | It is permeable |
| Impermeability | 0.6MPa, 120min, no It is permeable | 0.6MPa, 120min, no It is permeable | 0.6MPa, 120min, no It is permeable | 0.6MPa, 120min, no It is permeable | 0.6MPa, 120min, no It is permeable | 0.6MPa, 120min, thoroughly Water | It is permeable |
| When surface drying Between/h | 4 | 2 | 4 | 3 | 2 | 6 | 12 |
| When doing solid work Between/h | 12 | 16 | 10 | 18 | 13 | 23 | 48 |
| Film outward appearance | It is transparent | It is transparent | It is transparent | It is transparent | It is transparent | Whiten | Whiten |
Comparative sample 1(201610553980.7) embodiment 1 carry out data determination, comparative sample 2 is using 201410703140.5
Example 1 carries out data determination, as it can be seen from table 1 test data of the invention is better than the performance of documents.
Table 2 does not add 2,6- lutidines -4- carboxylate methyl ester
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Surface drying time/h | 9 | 5 | 7 | 8 | 7 |
| Do solid work the time/h | 24 | 28 | 29 | 32 | 38 |
Not plus 2, the surface drying of the film of 6- lutidines -4- carboxylate methyl ester and time raising is done solid work, display performance is poor.
Table 3 does not carry out the film properties of step 3,4,5,6
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| It is impermeable It is aqueous | 0.3MPa, 120min, it is permeable | 0.3MPa, 120min, it is permeable | 0.3MPa, 120min, it is permeable | 0.3MPa, 120min, It is waterproof | 0.3MPa, 120min, it is permeable |
| It is impermeable It is aqueous | 0.6MPa, 120min, it is permeable | 0.6MPa, 120min, it is permeable | 0.6MPa, 120min, it is permeable | 0.6MPa, 120min, It is waterproof | 0.6MPa, 120min is permeable |
| Outside film It sees | Whiten | Whiten | Whiten | Whiten | Whiten |
Not plus step 3,4,5,6 waterproofness decline, if the present invention unused fish-skin processing, water penetration and film outward appearance performance
It can decline.
If the chloro- n-butyl alcohol of 4- is not added by the present invention, it will increase the removing difficulty of film, influence the complete appearance of film
Property, therefore the chloro- n-butyl alcohol of 4- is removed convenient for curing agent and fish scale.
Table 4 does not add the film properties of dimethylaniline
Table 4 is not as can be seen that add the waterproof performance decline of dimethylaniline.
Table 5 does not add the film properties of six molybdic acids
Table 5 is not as can be seen that add the waterproof performance decline of six molybdic acids.
Table 6 does not add the film properties of tetrabutylammonium bromide
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Low-temperature bending/DEG C≤ | - 35, crackle | - 35, crackle | - 35 crackles | - 35, crackle | - 35, crackle |
As can be seen from Table 6, not plus the low temperature folding resistance of the film properties of tetrabutylammonium bromide decline, film, which is presented, in example has largely
Crackle.
Claims (5)
1. a kind of preparation method of waterproof aqueous polyurethane coating and finishing agent, it is characterised in that:
(1) equipped with stirring slurry, thermometer, condenser pipe 250ml three-necked flask in, by dihydric alcohol 18.4g, isocyanates
57.6g mixing under the conditions of existing for the catalyst dibutyltin dilaurylate 0.72g, 1 ~ 3h is reacted at 70 ~ 80 DEG C, is obtained
Base polyurethane prepolymer for use as A；
(2) dimethylolpropionic acid 17.3g is added into base polyurethane prepolymer for use as A, in 75 ~ 80 DEG C of 1 ~ 2h of reaction, triethylamine is added
8.9g carries out 30 ~ 60min of neutralization reaction, adds water 130g to carry out 1 ~ 2h of emulsification, and 2,6- lutidines -4- carboxylate methyl ester is added
0.6g, 85 DEG C of reaction temperature, reaction time 1h, regulation system pH are 7 ~ 8, obtain aqueous polyurethane coating；
3) (32g in total) will be peeled with the fish-skin of fish scale, be sequentially placed into mass concentration be 30%, 50%, 70%, 90%,
It is dehydrated in 100% graded ethanol, is then placed in the baking oven that temperature is 60 DEG C and dries, obtain the dry fish with fish scale
Skin；
4) it is according to mass ratio by dimethyl silicone polymer, curing agent, cure boosters and the chloro- n-butyl alcohol of 4-
6: 1: 0.1:0.01 ratio is mixed to get mixture (total weight 12g), then obtains mixture in step 3)
On fish-skin with fish scale one side, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 120 DEG C and solidifies 1 ~ 2 h
；After solidification, the mixture and fish-skin of dimethyl silicone polymer, curing agent, cure boosters and the chloro- n-butyl alcohol of 4- are removed, obtained
There is the cured dimethyl silicone polymer of fish scale antistructure and the mixture template of curing agent to the surface of replica fish scale；
5) by maleic anhydride 12g, 1 ~ 3g of nano-titanium dioxide, 1 ~ 3g of p-methyl benzenesulfonic acid, dimethylaniline 3.1g, six molybdic acids
1.7g, tetrabutylammonium bromide 0.3g, which are dissolved in 40 ~ 50g of water, obtains mixed solution, by ultrasound 15 minutes, stirs 2 ~ 3h, makes to mix
Solution is closed to be uniformly mixed；
6) mixed solution that step 5) obtains and the aqueous polyurethane coating that step 2 obtains are poured on what step 4) obtained
In template, with wavelength be 260nm ultraviolet light template on mixed solution 20min, make maleic anhydride and nano-silica
Change titanium crosslinks polymerization under the action of initiator p-methyl benzenesulfonic acid and obtains compound, and obtained compound and template are shelled
From, and repeated flushing into the water, unreacted maleic anhydride monomer is removed, the super thin of the biomimetic features of high mechanical strength is obtained
The underwater self-cleaning composite membrane of polymer of oil, as waterproof aqueous polyurethane coating and finishing agent.
2. a kind of preparation method of waterproof aqueous polyurethane coating and finishing agent as described in claim 1, the dihydric alcohol
For any one of polytetrahydrofuran ether glycol, polycarbonate glycol, 1,4- butanediol.
3. a kind of preparation method of waterproof aqueous polyurethane coating and finishing agent as described in claim 1, the isocyanates
For any one of '-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
4. a kind of preparation method of waterproof aqueous polyurethane coating and finishing agent as described in claim 1, the curing agent are
Poly(N-isopropylacrylamide), p-chlorotrichlormethyl, N, N- diethyl hydroxylamine any one.
5. a kind of preparation method of waterproof aqueous polyurethane coating and finishing agent as described in claim 1, the solidification synergy
Agent is 3- nitro -4- aminoanisole, 2- nitro -4- aminoanisole, 4,4'- oxo bis- (benzene sulfonyl chlorides), 2,4- dimethyl
Any one of acetoacetanilide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696262A (en) * | 2009-10-23 | 2010-04-21 | 华南理工大学 | Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents |
| CN102140218A (en) * | 2010-01-28 | 2011-08-03 | 中国科学院化学研究所 | Ultra-oleophobic underwater self-cleaning polymer composite film with biomimic structure and manufacturing method thereof |
-
2018
- 2018-11-21 CN CN201811394224.XA patent/CN109486403A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696262A (en) * | 2009-10-23 | 2010-04-21 | 华南理工大学 | Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents |
| CN102140218A (en) * | 2010-01-28 | 2011-08-03 | 中国科学院化学研究所 | Ultra-oleophobic underwater self-cleaning polymer composite film with biomimic structure and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
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| 夏征农等: "《大辞海·化工轻工纺织卷》", 31 August 2009, 上海辞书出版社 * |
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