CN106543881A - A kind of water polyacrylic acid modified polyurethane water-repellent paint and its preparation method and application - Google Patents
A kind of water polyacrylic acid modified polyurethane water-repellent paint and its preparation method and application Download PDFInfo
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- CN106543881A CN106543881A CN201610953902.6A CN201610953902A CN106543881A CN 106543881 A CN106543881 A CN 106543881A CN 201610953902 A CN201610953902 A CN 201610953902A CN 106543881 A CN106543881 A CN 106543881A
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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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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention belongs to aqueous waterproofing paint technical field, discloses a kind of water polyacrylic acid modified polyurethane water-repellent paint and its preparation method and application.The water-repellent paint includes the component of following mass parts meter：100 parts of water polyacrylic acid modified polyurethane copolymer emulsion, 0.1～0.5 part of defoamer, 0.1～0.5 part of ultraviolet absorber, 0.1～0.5 part of levelling agent, 0.1～0.5 part of antioxidant, 100～300 parts of filler, the wherein solid content of water polyacrylic acid modified polyurethane copolymer emulsion are 20%～60%.The present invention realizes the chemical modification of molecular level using polyacrylate to polyurethane, the advantage of polyacrylate and polyurethane is combined effectively, so that the water polyacrylic acid modified polyurethane water-repellent paint of the present invention had both had the advantages that polyacrylate water-repellent paint good weatherability, mechanical property were good, have the advantages that polyurethane water-proof paint pliability is good, adhesive force is big again.
Description
Technical field
The invention belongs to aqueous waterproofing paint technical field, more particularly to a kind of water polyacrylic acid modified polyurethane is prevented
Water paint and its preparation method and application.
Background technology
Water-repellent paint it is cured after formed waterproofing membrane have certain extensibility, elastoplasticity, crack resistance, impermeability and
Weatherability, thus waterproof can be played, prevent blending protective effect.It is widely used in building, and tunnel, furniture, road surface etc. are very
In the middle of extensive field.
Currently marketed coating is much solvent-borne type, containing substantial amounts of organic volatile (VOC), in production and use
During can a large amount of VOC are discharged in air, cause environmental pollution, at the same endanger people health.As people are protected to environment
The pay attention to day by day of shield, environmental regulation it is increasingly strict, it has been trend of the times to produce low VOC, environmentally friendly water paint.
Water polyacrylic acid class water-repellent paint and water-based polyurethane water-repellent paint are in the market using very many
Water-repellent paint.Water polyacrylic acid class water-repellent paint has the advantages that weather-proof alkali resistant, water-fast anti-powdering, but its attachment
Power is poor, and film easily comes off, and poor in flexibility, film not impact resistance.Aqueous polyurethane water-repellent paint have wearability it is good,
The big advantage of flexible oil resistant, adhesive force, then its weatherability and alkali resistance are poor, and hardness of film is not good enough.Aqueous poly- third
These weak points of olefin(e) acid esters and water-based polyurethane water-repellent paint have had a strong impact on their construction quality, limit it
Use range.Thus, mutually it is modified by polyacrylate and polyurethane, both are compound, realize having complementary advantages so as to obtain
The aqueous polyacrylamide acid modified polyurethane water-repellent paint being obviously improved to combination property will be the developing direction of water-repellent paint.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art and deficiency, the primary and foremost purpose of the present invention is to provide a kind of aqueous poly- third
Using polyacrylate, the ester modified polyurethane water-proof paint of olefin(e) acid, the water-repellent paint realize that to polyurethane the chemistry of molecular level changes
Property, the advantage of polyacrylate and polyurethane is effectively combined, both with polyacrylate water-repellent paint good weatherability, mechanical property
Can be good the advantages of, have the advantages that polyurethane water-proof paint pliability is good, adhesive force is big again, be a kind of ring for meeting development trend
Guarantor's type product.
Another object of the present invention is the preparation method for providing above-mentioned water polyacrylic acid modified polyurethane water-repellent paint.
The method introduces hydrophilic carboxyl and end inside polyurethane prepolymer by introducing hydroxyl inside polyacrylate prepolymer
NCO, then the terminal isocyanate group using hydroxyl and polyurethane prepolymer in random polypropylene acid esters prepolymer is anti-
Should, so as to realize both bondings, obtain water polyacrylic acid modified polyurethane water-repellent paint.
Still a further object of the present invention is to provide above-mentioned water polyacrylic acid modified polyurethane water-repellent paint in building, road
The application in the fields such as road, bridge.
The purpose of the present invention is realized by following proposal：
A kind of water polyacrylic acid modified polyurethane water-repellent paint, which includes the component of following mass parts meter：
Water polyacrylic acid modified polyurethane in described water polyacrylic acid modified polyurethane copolymer emulsion
With structure as shown below：
Wherein, R1For In one kind；
R2For H, CH3、CH2CH3In one kind；
R3For CH3、CH2CH3In one kind；
R4For the alkyl of 2～4 C；
R5、R6For the alkyl of 1～18 C；
R7、R8、R9For H or CH3；
N, m, k, x are 5～50 integer.
Described defoamer is preferably at least one in BYK-024, CA-2041, B-83, HT-530, BKY-019 etc..
Described ultra-violet absorber can be at least one in UV196, UV1130,2,4 dihydroxyl benzophenone etc..
Described antioxidant is at least one in 1010,300,3114.
Described levelling agent can be at least one in BYK-333, BKY-349, BYK-355 etc..
Described filler can be nano aluminium oxide, nano silicon, white carbon, silicon powder, wollastonite, titanium dioxide and light
At least one in the customary fillers such as matter calcium carbonate.
Described filler is preferably the mixture of silicon powder, wollastonite, titanium dioxide and precipitated calcium carbonate.
Described water polyacrylic acid modified polyurethane copolymer emulsion is prepared by following methods：
(1) synthesize the polyacrylate prepolymer containing hydroxyl：Under solvent existence condition, by (methyl) acrylate,
(methyl) crylic acid hydroxy ester, initiator mixing, then at 60～80 DEG C, reaction obtains final product synthesis for 4～8 hours containing hydroxyl
Polyacrylate prepolymer；
The mass ratio of (methyl) acrylate used, (methyl) crylic acid hydroxy ester, initiator and solvent in step (1)
For (80～96)：(4～20)：(2～6)：(100～200)；
(methyl) acrylate described in step (1) can be：(methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) propyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) isobutyl acrylate, (methyl) octadecyl acrylate, (first
Base) at least one in lauryl acrylate and (methyl) benzyl acrylate；Described (methyl) crylic acid hydroxy ester can be (first
Base) hydroxy-ethyl acrylate, at least one in (methyl) hydroxypropyl acrylate and (methyl) acrylic acid -4- hydroxybutyls；It is described
Initiator can be in the radical reaction initiator commonly used in the art such as azodiisobutyronitrile, ABVN at least one
Kind；Described solvent is used to provide solution reaction environment, can be at least one in acetone, butanone, 2 pentanone and propione.
(2) synthesize the polyurethane prepolymer containing terminal isocyanate group：Under solvent existence condition, by diisocyanate,
Polyether Glycols, double hydroxycarboxylic acid mixing, then at 60～80 DEG C, 4～8 hours reaction time was obtained final product containing isocyanate terminated
The polyurethane prepolymer of base；
In step (2) mass ratio of diisocyanate used, polyether Glycols, double hydroxycarboxylic acids and solvent for (20～
80)：(16～65)：(4～15)：(100～200)；
Diisocyanate described in step (2) is preferably toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene
Dimethylene diisocyanate, 1,5- naphthalene diisocyanates, 4- Methylcyclohexyl diisocyanates, two isocyanide of dicyclohexyl methyl hydride
At least one in acid esters, hexamethylene diisocyanate and IPDI；Described polyether Glycols are polyethers
At least one in N210, polyethers N220 and polyethers L44；Described double hydroxycarboxylic acids be 2,2- dihydromethyl propionic acids, 2,2- bis-
At least one in hydroxymethylbutyrate, 2,4- dihydroxy-benzoic acids, 2,6- dihydroxy-benzoic acids etc.；Described solvent is used to provide
Solution reaction environment, can be at least one in acetone, butanone, 2 pentanone and propione, and in described solvent and step (1)
Described solvent is same.
(3) preparation of water polyacrylic acid modified polyurethane copolymer：Containing hydroxyl poly- third that step (1) is obtained
The mixing of the polyurethane prepolymer containing terminal isocyanate group that olefin(e) acid ester prepolymer and step (2) are obtained, then at 60～80 DEG C
Lower reaction obtains final product polyacrylate modified polyurethane copolymer in 4～8 hours；
In step (3), the polyacrylate prepolymer containing hydroxyl and the polyurethane containing terminal isocyanate group used are pre-
The mass ratio of polymers is (33～50)：(50～67).
(4) preparation of water polyacrylic acid modified polyurethane copolymer emulsion：By step (3) prepare it is aqueous poly-
It is that deionized water emulsification is subsequently adding between 7～8 that polymerization of acrylic modified polyurethane copolymer triethylamine is neutralized to pH value, finally
Revolving removes the solvent of the inside, you can obtain water polyacrylic acid modified polyurethane emulsion, and emulsion solid content is 20%～
60%.
A kind of preparation method of above-mentioned water polyacrylic acid modified polyurethane water-repellent paint, specifically includes following steps：
Above-mentioned each component is added in container under normal temperature, be uniformly mixed, that is, prepare water polyacrylic acid modified polyurethane
Water-repellent paint.
Above-mentioned water polyacrylic acid modified polyurethane water-repellent paint realizes molecule to polyurethane using polyacrylate
The chemical modification of level, effectively combines the advantage of polyacrylate and polyurethane, both resistance to polyacrylate water-repellent paint
The advantages of good, mechanical property of time property is good, has the advantages that polyurethane water-proof paint pliability is good, adhesive force is big again, is a kind of symbol
The environmentally friendly machine of development trend is closed, the fields such as building, road, bridge are can be applicable to.
The present invention mechanism be：
The present invention introduces hydrophilic by introducing hydroxyl inside polyacrylate prepolymer inside polyurethane prepolymer
Carboxyl, then using the terminal isocyanate group reaction of hydroxyl and polyurethane prepolymer in random polypropylene acid esters prepolymer, so as to
Both bondings are realized, the chemical modification of molecular level is realized to polyurethane using polyacrylate, polypropylene is effectively combined
The advantage of acid esters and polyurethane so that the water polyacrylic acid modified polyurethane water-repellent paint of the present invention had both had polyacrylic acid
Ester water-repellent paint good weatherability, the advantages of mechanical property is good, it is excellent to have that polyurethane water-proof paint pliability is good, adhesive force is big again etc.
Point, is a kind of environmentally friendly machine for meeting development trend.
The present invention is had the following advantages and beneficial effect relative to prior art：
This experiment realizes polyacrylate to being modified in polyurethane molecular level by chemical method, and what is obtained is aqueous
Polyacrylate modified polyurethane water-repellent paint had both had the advantages that the flexible good, adhesive force of polyurethane was big, had polyacrylic acid again
Ester is weather-proof, the advantage of water-tolerant.Water polyacrylic acid modified polyurethane water-repellent paint obtained in of the invention is being prepared and is being made
With during, organic volatile is less, and environmental pollution is little, environmental protection.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
In embodiment, agents useful for same can be routinely buied from market if no special instructions.
Embodiment 1
(1) by 42.5 weight portion of isoflurane chalcone diisocyanate of eliminating water, polyether Glycols N210 (molecular weight is 1000)
48.4 weight portions, 2,2- dihydromethyl propionic acids, 9.1 weight portion, 100 weight portion of butanone are added in reaction vessel, are heated to 80
DEG C, react 5h, you can obtain base polyurethane prepolymer for use as.
(2) by 87.4 weight portion of methyl methacrylate of eliminating water, 12.6 weight portion of hydroxyethyl methacrylate, azo two
3 weight portion of isobutyronitrile, 100 weight portion of butanone are added in reactor, are heated to 80 DEG C, react 5h, you can obtain polyacrylic acid
Ester performed polymer.
(3) 100 weight portion of base polyurethane prepolymer for use as obtained above and 55 weight portion of polyacrylate performed polymer are added to
In reactor, 80 DEG C are heated to, react 5h.After reaction terminates, after which is cooled to room temperature, triethylamine is added in above-mentioned product
Its pH value is neutralized to for 8.Then add the deionized water of 184 weight portions again inwards, stir half an hour.Finally, at 60 DEG C
Revolving, removes the butanone of the inside, that is, obtain the emulsion of water polyacrylic acid modified polyurethane, and the solid content of emulsion is 30%.
(4) precipitated calcium carbonate is added in 100 weight portions water polyacrylic acid modified polyurethane emulsion obtained above
50 weight portions, 70 weight portion of silicon powder, 60 weight portion of titanium dioxide, 60 weight portion of wollastonite, 0.5 weight portions of defoamer HT-530,
0.1 weight portions of levelling agent BYK-333,0.1 weight portion of antioxidant 1010,0.1 weight portions of ultraviolet absorber UV196.Mixing
Afterwards, it is uniform by strength mechanical agitation, you can to obtain water polyacrylic acid modified polyurethane water-repellent paint.
Embodiment 2
(1) by 39.7 weight portion of toluene di-isocyanate(TDI) of eliminating water, polyether Glycols L44 (molecular weight is 2200) 52.9 weights
Amount part, 2,2- dimethylolpropionic acids, 7.4 weight portion, 100 weight portion of 2 pentanone are added in reaction vessel, are heated to 70 DEG C, instead
Answer 6h, you can obtain base polyurethane prepolymer for use as.
(2) by 89.6 weight portion of Isobutyl methacrylate of eliminating water, 10.4 weight portion of hydroxyethyl methacrylate, azo
3 weight portion of bis-isobutyronitrile, 100 weight portion of 2 pentanone are added in reactor, are heated to 70 DEG C, react 6h, you can obtain poly- third
Olefin(e) acid ester performed polymer.
(3) 100 weight portion of base polyurethane prepolymer for use as obtained above and 60 weight portion of polyacrylate performed polymer are added to
In reactor, 70 DEG C are heated to, react 6h.Reaction terminates, after which is cooled to room temperature, in adding triethylamine in above-mentioned product
With to its pH value be 8.Then 83 parts by weight of deionized water are added again inwards, half an hour is stirred.Finally, rotate at 70 DEG C,
The 2 pentanone of the inside is removed, that is, obtains the emulsion of water polyacrylic acid modified polyurethane, the solid content of emulsion is 50%.
(4) precipitated calcium carbonate is added in 100 weight portions water polyacrylic acid modified polyurethane emulsion obtained above
80 weight portions, 60 weight portion of silicon powder, 40 weight portion of titanium dioxide, 50 weight portion of wollastonite, 0.4 weight of defoamer BKY-019
Part, 0.2 weight portions of levelling agent BYK-333,0.2 weight portion of antioxidant 1010,0.2 weight portions of ultraviolet absorber UV196.It is mixed
It is after conjunction, uniform by strength mechanical agitation, you can to obtain water polyacrylic acid modified polyurethane water-repellent paint.
Embodiment 3
(1) by 34.5 weight portion of '-diphenylmethane diisocyanate of eliminating water, polyether Glycols N220 (molecular weight is 2000)
55 weight portions, 2,2- dimethylolpropionic acids, 10.5 weight portion, 100 weight portion of propione are added in reaction vessel, are heated to 80
DEG C, react 5h, you can obtain base polyurethane prepolymer for use as.
(2) by 87.7 weight portion of EMA of eliminating water, 12.3 weight portion of hydroxy propyl methacrylate, azo two
3 weight portion of different heptonitrile, 100 weight portion of propione are added in reactor, are heated to 80 DEG C, react 5h, you can obtain polypropylene
Acid esters performed polymer.
(3) 100 weight portion of base polyurethane prepolymer for use as obtained above and 75 weight portion of polyacrylate performed polymer are added to
In reactor, 80 DEG C are heated to, react 5h.After reaction terminates, after which is cooled to room temperature, triethylamine is added in above-mentioned product
Its pH value is neutralized to for 8.Then add the deionized water of 134 weight portions again inwards, stir half an hour.Finally, at 75 DEG C
Revolving, removes the propione of the inside, that is, obtains the emulsion of water polyacrylic acid modified polyurethane, and the solid content of emulsion is
40%.
(4) precipitated calcium carbonate is added in 100 weight portions water polyacrylic acid modified polyurethane emulsion obtained above
40 weight portions, 60 weight portion of silicon powder, 50 weight portion of titanium dioxide, 30 weight portion of wollastonite, 0.3 weight of defoamer CA-2041
Part, 0.3 weight portions of levelling agent BKY-349,0.2 weight portion of antioxidant 300,0.2 weight portions of ultraviolet absorber UV196.Mixing
Afterwards, it is uniform by strength mechanical agitation, you can to obtain water polyacrylic acid modified polyurethane water-repellent paint.
Embodiment 4
(1) by 37.1 weight portion of 1,5- naphthalene diisocyanates of eliminating water, polyether Glycols N220 (molecular weight is 2000)
53.7 weight portions, 2,2- dimethylolpropionic acids, 9.2 weight portion, 100 weight portion of butanone are added in reaction vessel, are heated to 80
DEG C, react 5h, you can obtain base polyurethane prepolymer for use as.
(2) by 93.2 weight portion of EHMA of eliminating water, 6.8 weight portion of methacrylic acid -4- hydroxybutyls,
3 weight portion of azodiisobutyronitrile, 100 weight portion of butanone are added in reactor, are heated to 80 DEG C, react 5h, you can gathered
Acrylate prepolymer body.
(3) 100 weight portion of base polyurethane prepolymer for use as obtained above and 80 weight portion of polyacrylate performed polymer are added to
In reactor, 80 DEG C are heated to, react 5h.After reaction terminates, after which is cooled to room temperature, triethylamine is added in above-mentioned product
Its pH value is neutralized to for 8.Then add the deionized water of 63 weight portions again inwards, stir half an hour.Finally, in 70 DEG C of backspins
Steam, remove the fourth pentanone of the inside, that is, obtain the emulsion of water polyacrylic acid modified polyurethane, the solid content of emulsion is 60%.
(4) precipitated calcium carbonate is added in 100 weight portions water polyacrylic acid modified polyurethane emulsion obtained above
70 weight portions, 50 weight portion of silicon powder, 40 weight portion of titanium dioxide, 70 weight portion of wollastonite, 0.5 weight portions of defoamer HT-530,
0.3 weight portions of levelling agent BKY-349,0.1 weight portion of antioxidant 1010,0.1 weight portions of ultraviolet absorber UV196.Mixing
Afterwards, it is uniform by strength mechanical agitation, you can to obtain the water-repellent paint of water polyacrylic acid modified polyurethane.
Embodiment 5
(1) by 34.6 weight portion of 4- Methylcyclohexyl diisocyanates of eliminating water, polyether Glycols L44, (molecular weight is
2200) 53.3 weight portions, 2,4- dihydroxy-benzoic acids, 12.1 weight portion, 100 weight portion of 2 pentanone are added in reaction vessel, plus
Heat reacts 6h, you can obtain base polyurethane prepolymer for use as to 75 DEG C.
(2) by 91.1 weight portion of methyl methacrylate of eliminating water, 8.9 weight portion of hydroxy propyl methacrylate, azo two
3 weight portion of isobutyronitrile, 100 weight portion of 2 pentanone are added in reactor, are heated to 75 DEG C, react 6h, you can obtain polypropylene
Acid esters performed polymer.
(3) 100 weight portion of base polyurethane prepolymer for use as obtained above and 90 weight portion of polyacrylate performed polymer are added to
In reactor, 75 DEG C are heated to, react 6h.After reaction terminates, after which is cooled to room temperature, triethylamine is added in above-mentioned product
Its pH value is neutralized to for 8.Then add the deionized water of 145 weight portions again inwards, stir half an hour.Finally, at 65 DEG C
Revolving, removes the 2 pentanone of the inside, that is, obtains the emulsion of water polyacrylic acid modified polyurethane, and the solid content of emulsion is
40%.
(4) precipitated calcium carbonate is added in 100 weight portions water polyacrylic acid modified polyurethane emulsion obtained above
60 weight portions, 50 weight portion of silicon powder, 70 weight portion of titanium dioxide, 40 weight portion of wollastonite, 0.4 weight portions of defoamer B-83, stream
Flat 0.1 weight portions of agent levelling agent BYK-355,0.2 weight portion of antioxidant 3114,0.2 weight portions of ultraviolet absorber UV1130.
It is after mixing, uniform by strength mechanical agitation, you can to obtain water polyacrylic acid modified polyurethane water-repellent paint.
Embodiment 6
(1) by 37.8 weight portion of 4- Methylcyclohexyl diisocyanates of eliminating water, polyether Glycols N210, (molecular weight is
1000) 51.7 weight portions, 2,4- dihydroxy-benzoic acids, 11.5 weight portion, 100 weight portion of butanone are added in reaction vessel, heating
To 75 DEG C, 6h is reacted, you can obtain base polyurethane prepolymer for use as.
(2) by 87.9 weight portion of methyl methacrylate of eliminating water, 12.1 weight portion of methacrylic acid -4- hydroxybutyls,
3 weight portion of ABVN, 100 weight portion of butanone are added in reactor, are heated to 75 DEG C, react 6h, you can gathered
Acrylate prepolymer body.
(3) 100 weight portion of base polyurethane prepolymer for use as obtained above and 100 weight portion of polyacrylate performed polymer are added to
In reactor, 75 DEG C are heated to, react 6h.After reaction terminates, after which is cooled to room temperature, triethylamine is added in above-mentioned product
Its pH value is neutralized to for 8.Then add the deionized water of 103 weight portions again inwards, stir half an hour.Finally, at 65 DEG C
Revolving, removes the butanone of the inside, that is, obtain the emulsion of water polyacrylic acid modified polyurethane, and the solid content of emulsion is 50%.
(4) precipitated calcium carbonate is added in 100 weight portions water polyacrylic acid modified polyurethane emulsion obtained above
50 weight portions, 70 weight portion of silicon powder, 60 weight portion of titanium dioxide, 40 weight portion of wollastonite, 0.4 weight portions of defoamer BYK024,
0.3 weight portions of levelling agent levelling agent BYK-355,0.2 weight portion of antioxidant 3114,0.2 weight portions of ultraviolet absorber UV1130.
It is after mixing, uniform by strength mechanical agitation, you can to obtain water polyacrylic acid modified polyurethane water-repellent paint.
Embodiment 7
The performance of the water polyacrylic acid modified polyurethane water-repellent paint prepared to embodiment 1～6 is tested.
The standard being first according in GB GB/T19250-2003 prepares batten and film, tests its tensile strength and elongation at break
Deng.Testing standard：(1) tensile strength：GB/T19250-2003, draw speed are (500 ± 50) mm/min；(2) extension at break
Rate：GB/T19250-2003, draw speed are (500 ± 50) mm/min；(3) surface drying time：GB/T19250-2003；(4) it is solid
Content：GB/T19250-2003；(5) impermeability：GB/T19250-2003.As a result see the table below shown in 1.
The performance test number of the water polyacrylic acid modified polyurethane water-repellent paint that 1 embodiment 1～6 of table is prepared
According to
Can be obtained by above-mentioned table 1, the water polyacrylic acid modified polyurethane water-repellent paint film for obtaining has higher
Tensile strength and elongation at break, and surface drying time is also shorter, meets the requirement of GB.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of water polyacrylic acid modified polyurethane water-repellent paint, it is characterised in that the component comprising following mass parts meter：
The solid content of wherein described water polyacrylic acid modified polyurethane copolymer emulsion is 20～60%.
2. water polyacrylic acid modified polyurethane water-repellent paint according to claim 1, it is characterised in that described water
Water polyacrylic acid modified polyurethane in property polyacrylate modified polyurethane copolymer emulsion has knot shown below
Structure：
Wherein, R1For In one kind；
R2For H, CH3、CH2CH3In one kind；
R3For CH3、CH2CH3In one kind；
R4For the alkyl of 2～4 C；
R5、R6For the alkyl of 1～18 C；
R7、R8、R9For H or CH3；
N, m, k, x are 5～50 integer.
3. water polyacrylic acid modified polyurethane water-repellent paint according to claim 1 and 2, it is characterised in that：
Described defoamer is at least one in BYK-024, CA-2041, B-83, HT-530, BKY-019；
Described ultra-violet absorber is UV196, UV1130, at least one in 2,4 dihydroxyl benzophenone；
Described antioxidant is at least one in 1010,300,3114；
Described levelling agent is at least one in BYK-333, BKY-349, BYK-355；
Described filler is nano aluminium oxide, nano silicon, white carbon, silicon powder, wollastonite, titanium dioxide and lightweight carbonic acid
At least one in calcium.
4. water polyacrylic acid modified polyurethane water-repellent paint according to claim 1 and 2, it is characterised in that described
Water polyacrylic acid modified polyurethane copolymer emulsion is prepared by following methods：
(1) synthesize the polyacrylate prepolymer containing hydroxyl：Under solvent existence condition, by (methyl) acrylate, (first
Base) crylic acid hydroxy ester, initiator mixing, then at 60～80 DEG C reaction obtain final product within 4～8 hours synthesis containing hydroxyl poly- third
Olefin(e) acid ester prepolymer；
(2) synthesize the polyurethane prepolymer containing terminal isocyanate group：Under solvent existence condition, by diisocyanate, polyethers
Dihydroxylic alcohols, double hydroxycarboxylic acid mixing, then at 60～80 DEG C, 4～8 hours reaction time was obtained final product containing terminal isocyanate group
Polyurethane prepolymer；
(3) preparation of water polyacrylic acid modified polyurethane copolymer：The polyacrylic acid containing hydroxyl that step (1) is obtained
The mixing of the polyurethane prepolymer containing terminal isocyanate group that ester prepolymer and step (2) are obtained, it is then anti-at 60～80 DEG C
Answer 4～8 hours and obtain final product water polyacrylic acid modified polyurethane copolymer；
(4) preparation of water polyacrylic acid modified polyurethane copolymer emulsion：The aqueous polyacrylamide that step (3) is prepared
It is, between 7～8, to be subsequently adding deionized water emulsification, finally revolve that acid esters modified polyurethane copolymer triethylamine is neutralized to pH value
The solvent of the inside is evaporated off, that is, obtains water polyacrylic acid modified polyurethane emulsion, emulsion solid content is 20%～60%.
5. water polyacrylic acid modified polyurethane water-repellent paint according to claim 4, it is characterised in that：
In step (1), the mass ratio of (methyl) acrylate used, (methyl) crylic acid hydroxy ester, initiator and solvent is
(80～96)：(4～20)：(2～6)：(100～200)；
In step (2), the mass ratio of diisocyanate used, polyether Glycols, double hydroxycarboxylic acids and solvent is (20～80)：
(16～65)：(4～15)：(100～200)；
Polyacrylate prepolymer containing hydroxyl used and the polyurethane prepolymer containing terminal isocyanate group in step (3)
Mass ratio be (33～50)：(50～67).
6. water polyacrylic acid modified polyurethane water-repellent paint according to claim 4, it is characterised in that：
(methyl) acrylate described in step (1) is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid propyl ester, (methyl) Isooctyl acrylate monomer, (methyl) isobutyl acrylate, (methyl) octadecyl acrylate, (methyl) propylene
At least one in sour lauryl and (methyl) benzyl acrylate；Described (methyl) crylic acid hydroxy ester is (methyl) acrylic acid
At least one in hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate and (methyl) acrylic acid -4- hydroxybutyls；Described initiator is
At least one in azodiisobutyronitrile, ABVN；During described solvent is acetone, butanone, 2 pentanone and propione
At least one.
7. water polyacrylic acid modified polyurethane water-repellent paint according to claim 4, it is characterised in that：
Diisocyanate described in step (2) is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne
Diisocyanate, 1,5- naphthalene diisocyanates, 4- Methylcyclohexyl diisocyanates, dicyclohexyl methyl hydride diisocyanate, 1,
At least one in hexamethylene-diisocyanate and IPDI；Described polyether Glycols are polyethers N210, are gathered
At least one in ether N220 and polyethers L44；Described double hydroxycarboxylic acids be 2,2- dihydromethyl propionic acids, 2,2- dihydroxymethyl fourths
At least one in acid, 2,4- dihydroxy-benzoic acids, 2,6- dihydroxy-benzoic acids；Described solvent is acetone, butanone, 2 pentanone
With at least one in propione, and described solvent and the solvent described in step (1) are same.
8. a kind of water polyacrylic acid modified polyurethane water-repellent paint according to any one of claim 1～7, its feature
It is to comprise the following steps：
By water polyacrylic acid modified polyurethane copolymer emulsion, defoamer, ultraviolet absorber, levelling agent, antioxygen under normal temperature
During agent, filler add container, it is uniformly mixed, that is, prepares water polyacrylic acid modified polyurethane water-repellent paint.
9. the water polyacrylic acid modified polyurethane water-repellent paint according to any one of claim 1～7 is in building, road
Road, the application in bridge field.
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| CN109796866A (en) * | 2019-02-14 | 2019-05-24 | 天津通用科技有限公司 | A kind of ground waterproof coating and preparation method thereof |
| CN109881481A (en) * | 2019-01-31 | 2019-06-14 | 刘方方 | A kind of waterproof fabric |
| CN110511662A (en) * | 2019-08-16 | 2019-11-29 | 江苏凯伦建材股份有限公司 | A kind of double-composition polyurethane waterproof paint and preparation method thereof |
| CN110746878A (en) * | 2019-11-19 | 2020-02-04 | 合众（佛山）化工有限公司 | High-hardness anti-sagging polyurethane water-based functional coating |
| CN111042532A (en) * | 2019-12-24 | 2020-04-21 | 广东嘉泰建设有限公司 | Construction method for preventing water on ground |
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| CN109881481B (en) * | 2019-01-31 | 2021-07-27 | 东莞职业技术学院 | Waterproof fabric |
| CN109796866A (en) * | 2019-02-14 | 2019-05-24 | 天津通用科技有限公司 | A kind of ground waterproof coating and preparation method thereof |
| CN110511662A (en) * | 2019-08-16 | 2019-11-29 | 江苏凯伦建材股份有限公司 | A kind of double-composition polyurethane waterproof paint and preparation method thereof |
| CN110746878A (en) * | 2019-11-19 | 2020-02-04 | 合众（佛山）化工有限公司 | High-hardness anti-sagging polyurethane water-based functional coating |
| CN111042532A (en) * | 2019-12-24 | 2020-04-21 | 广东嘉泰建设有限公司 | Construction method for preventing water on ground |
| CN114232382A (en) * | 2021-11-16 | 2022-03-25 | 苏州美盈森环保科技有限公司 | Printable water-retaining coating, preparation method and application |
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