CN106010202A - Preparation method of aqueous polyurethane coating with modified kaolin as filler - Google Patents
Preparation method of aqueous polyurethane coating with modified kaolin as filler Download PDFInfo
- Publication number
- CN106010202A CN106010202A CN201610640316.6A CN201610640316A CN106010202A CN 106010202 A CN106010202 A CN 106010202A CN 201610640316 A CN201610640316 A CN 201610640316A CN 106010202 A CN106010202 A CN 106010202A
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- CN
- China
- Prior art keywords
- aqueous polyurethane
- filler
- modified kaolin
- kaolin
- polyurethane coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
-
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of an aqueous polyurethane coating with modified kaolin as a filler. The preparation method comprises (1) dispersing 8-12g of uncalcined kaolin and 0.12-0.15g of a titanate coupling agent in 15-20ml of anhydrous ethanol, grinding the dispersion for 30-60 minutes, carrying out drying and recovering ethanol so that hydrophilic modified kaolin is obtained, (2) mixing 78-85g of aqueous polyurethane, 15-21g of modified kaolin, 0.5g of a defoaming agent and 0.5-1.5g of a thickening agent and carrying out ball milling dispersion for 30-60min to obtain the aqueous polyurethane coating with modified kaolin as a filler. The modified kaolin has a suspension rate of 85-92% in water. The preparation method has the advantages of use of the cheap filler, simple ball milling process, low energy consumption and environmental protection. By adding a high amount of hydrophilic modified kaolin to the aqueous polyurethane coating, the comprehensive performances of the coating is obviously improved. The aqueous polyurethane coating film is hard and strong in an adhesive force and has good water resistance and weatherability.
Description
Technical field
The present invention relates to coating application, a kind of aqueous polyurethane with modified kaolin as filler
The preparation method of coating.
Background technology
Aqueous polyurethane coating is with water-dispersible polyurethane resin as base material, with water during construction application
Make a kind of water paint of dispersant.Have that paint film physical and mechanical properties is good, corrosion resistance good, Ke Yi
The advantage such as room temperature or even curing at low temperatures；By the selection of raw material, the cooperation of component and the application of auxiliary agent,
Produce for the different coating of the performance characteristics of different field.Aqueous is gathered compared with traditional solvent based coating
The great advantage of urethane coating is to greatly reduce the consumption of volatile organic solvent or substantially eliminate solvent
Existence, and meet environmental requirement.
Kaolin is extensively applied, no in the industries such as plastics, coating, rubber as filler or functional filler
Only can reduce the cost of organic polymer goods, it is often more important that its mechanical performance, heat stability can be improved
Deng.Kaolin is carried out surface hydrophilic modification, Kaolin hydrophilic can be improved, improve Kaolin and gather in aqueous
Stablizing in urethane coating, increases its addition.When Kaolin interpolation reaches a certain amount of and is uniformly dispersed,
Polymeric matrix and clay layer have the planar orientation effect of good combination and clay layer, these lamellas pair
It is impervious for hydrone and monomer molecule, forces solute to pass through around silicate particles and bend
Path could pass through thin film, improve the organic channel length of diffusion, make aqueous polyurethane glued membrane show
The barrier of good dimensional stability, hydrone and heat.
After Kaolin surface modification, add in coating, it has also become the application that Kaolin is the most rising
One of field.At present, the coating that Kaolin is prepared as filler is more: Guan Junfang etc. by Kaolin, 16
The mixture of alkyl trimethyl ammonium bromide, machine oil and silane, titanate esters are put into stirring in high-speed mixer and are prepared
Modified kaolin product.In the method, titanate esters, silane coupler serve as a connection, and connect organic facies machine oil
With inorganic phase Kaolin so that kaolin surface coated by hydrophobic group.The modified kaolin table that the method prepares
Face oleophilic drainage, is suitable for use in rubber, plastics and solvent based coating, is coated with at aqueous polyurethane if applying
Material then has the compatibility is poor, obvious shortcoming of reuniting.
Yin Lisong etc. are compounded by the Ludox of alkali silicate Yu small particle and can be formed in film forming procedure
Si-O-Si derivatized polymers, adds the filming performance that can improve coating in organic polymeric emulsions to.
The Si-O-Si derivatized polymers that the method is formed plays the effect of physical crosslinking point in polymer emulsion,
Emulsion viscosity is increased dramatically, brings difficulty to the spraying of later stage coating.
Imperial court sea is with calcined kaolin, roasting kieselguhr, sodium bentonite and waterglass as base material, in proportion
Add aqueous based carrier and be prepared as coating.The Kaolin that the method is used is calcined kaolin, although calcining kaolinite
Soil surface has certain hydrophilic, but the density of the hydrophilic group on surface is limited makes calcined kaolin exist
Disperseing uneven in water paint, film is easy to crack, hardness heterogeneity.
Lu Zhi good general's polyurethane resin, politef, Kaolin, dimethicone, ethyl acetate, third
A kind of wear-resistant polyurethane coating it is prepared into after glycol mix and blend.Prepared by the method is that solvent borne polyurethane is coated with
Material, in film forming procedure, a large amount of organic solvents of volatilization are bigger to environmental hazard.
Summary of the invention
Technical problem solved by the invention is to provide a kind of aqueous polyurethane with modified kaolin as filler
The preparation method of coating, to solve the problem in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions: one with modified kaolin is
The preparation method of the aqueous polyurethane coating of filler, comprises the following steps:
(1) 8 12g Kaolin, the 0.12 0.15g titanate coupling agent without calcining is scattered in
In 15 20ml dehydrated alcohol, grind 30 60min, dry and reclaim ethanol, prepare hydrophilic modifying kaolinite
Soil；
(2) by 78～85g aqueous polyurethanes, 15～21g modified kaolin, 0.5g defoamer and 0.5～
1.5g thickening agent mixes, and ball milling disperses 30 60min, obtains the poly-ammonia of the aqueous with modified kaolin as filler
Ester paint.
The described aqueous polyurethane coating with modified kaolin as filler, the hot strength of its glued membrane be 15～
24MPa, elongation at break are 412～448%, hardness 64～82 Shao A, water absorption rate 1.3～1.82%, maximum
Heat decomposition temperature 359～379 DEG C.
Described titanate coupling agent is double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters.
Described aqueous polyurethane is the one in water-based aliphaic polyurethane, aromatic waterborne polyurethane or two
Kind, solid content is 30～55%, emulsion viscosity 30～100mPas；Particle diameter distribution 60～200nm.
Described defoamer is one or both in organosilicon, vegetable oil defoamer.
Described thickening agent is in organobentonite, butyl acetate cellulose, non-ion aqueous polyurethane
Plant or several mixing.
Compared with disclosed technology, there is advantages below in the present invention:
(1) modified kaolin that the present invention prepares suspensibility in water reaches 85～92%.
(2) modified kaolin that the present invention prepares can reach higher addition in aqueous polyurethane coating,
And it is uniformly dispersed that (as shown in adnexa 1, the stereoscan photograph of film surface shows, through modified kaolinite
Soil content in glued membrane reaches good dispersion when 18%, and observation scope does not has obvious agglomeration；Partial enlargement
Figure, it can be seen that the lamella of modified kaolin is embedded in polyurethane matrix, two-phase interface obscure, this be by
In Kaolin with active group, it is simple to coupling agent, as bridge, connects kaolin particle and polyurethane chain,
Strengthen two-phase interface adhesive force), coating storage stability good.(imitate incorporated by reference to Fig. 1 analytic explanation Advantageous
Really)
(3) hydrophilic modifying Kaolin of the present invention prepares aqueous polyurethane coating as filler: filler is inexpensive, and
Ball-milling technology is simple, low power consuming, environmental protection.
(4) the hydrophilic modifying Kaolin of higher amount adds in aqueous polyurethane coating, the combination property of coating
Improve substantially: aqueous polyurethane coating glued membrane prepared by the present invention is hard and bonding force strong, resistance to water, weather-proof
Property is preferable.Along with titanate esters modified kaolin addition in aqueous polyurethane increases, the hot strength of glued membrane
Being increased to 24MPa by 15MPa, fracture elongation is increased to 448% by 408%, and hardness is increased to by Shao A 53
82, resistance to water is soaked water absorption rate 6.8% by 24h clear water and is reduced to 1.31%.
Accompanying drawing explanation
After Fig. 1 is the chilled brittle failure of aqueous polyurethane coating film of the present invention, the microscopic appearance figure of the plane of disruption.
Detailed description of the invention
In order to make the technological means of the present invention, creation characteristic, workflow, using method reach purpose and merit
Effect is easy to understand, and below in conjunction with the embodiment of the present invention, enters the technical scheme in the embodiment of the present invention
Row clearly and completely describes, it is clear that described embodiment is only a part of embodiment of the present invention, and
It is not all, of embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under creative work premise, broadly falls into the scope of protection of the invention.
In following example
Double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters provides the (trade mark for Nanjing Neng De Chemical Co., Ltd.
TCA-311W)；
Laboratory synthesis water-based aliphaic polyurethane, its soft section based on N210, isocyanates is IPDI；
Aromatic waterborne polyurethane its soft section is N210, and isocyanates is TDI.
Defoamer: organosilicon, vegetable oil defoamer
Thickening agent: for organobentonite, butyl acetate cellulose or non-ion aqueous polyurethane.
Embodiment 1
The preparation method of a kind of aqueous polyurethane coating with modified kaolin as filler, comprises the following steps:
(1) by without the 60g Kaolin of calcining, 0.9g pair of (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters
It is scattered in 120ml dehydrated alcohol；Grind 1h under the conditions of drum's speed of rotation 200r/min, reclaim dehydrated alcohol,
In 50 DEG C of baking ovens, it is dried 24h, prepares hydrophilic modifying Kaolin.
(2) by aqueous polyurethane 85g, hydrophilic modifying Kaolin 15g, waterborne organic silicon defoamer 0.5g and
Non-ion aqueous polyurethane thickening agent 1.5g mixes；Ball milling under the conditions of planetary ball mill rotating speed 200r/min
Dispersion 1h, obtains the aqueous polyurethane coating that modified kaolin is filler；Its hot strength is 19MPa, breaks
Split percentage elongation be 443%, hardness Shao A68, water absorption rate 2.47%, maximum heat decomposition temperature 359 DEG C.
Embodiment 2
The preparation method of a kind of aqueous polyurethane coating with modified kaolin as filler, comprises the following steps:
(1) by without the Kaolin of 60g calcined, double (dioctylphyrophosphoric acid acyloxy) ethylene titaniums of 0.9g
Acid esters is scattered in the dehydrated alcohol of 120ml；Grind 1h under the conditions of drum's speed of rotation 200r/min, reclaim nothing
Water-ethanol, in 50 DEG C of baking ovens, is dried 24h, prepares hydrophilic modifying Kaolin.
(2) by polyaminoester emulsion 82g, hydrophilic modifying Kaolin 18g, waterborne organic silicon defoamer 0.5g and
Non-ion aqueous polyurethane thickening agent 1g mixes；Under the conditions of planetary ball mill rotating speed 200r/min, ball milling divides
Dissipate 1.5h, obtain the aqueous polyurethane coating that modified kaolin is filler；Its hot strength be 20.7MPa,
Elongation at break is 448%, hardness Shao A75, water absorption rate 1.64%, maximum heat decomposition temperature 371 DEG C.
Embodiment 3
The preparation method of a kind of aqueous polyurethane coating with modified kaolin as filler, comprises the following steps:
(1) by without the Kaolin of 60g calcined, double (dioctylphyrophosphoric acid acyloxy) ethylene titaniums of 0.9g
Acid esters is scattered in the dehydrated alcohol of 120ml；Grind 1h under the conditions of drum's speed of rotation 200r/min, reclaim nothing
Water-ethanol, in 50 DEG C of baking ovens, is dried 24h, prepares hydrophilic modifying Kaolin..
(2) by polyaminoester emulsion 78g, hydrophilic modifying Kaolin 22g, waterborne organic silicon defoamer 0.5g and
Non-ion aqueous polyurethane thickening agent 0.5g mixes；Ball milling under the conditions of planetary ball mill rotating speed 200r/min
Dispersion 2h, obtains the aqueous polyurethane coating that modified kaolin is filler；Its hot strength is 24MPa, breaks
Split percentage elongation be 420%, hardness Shao A82, water absorption rate 1.31%, maximum heat decomposition temperature 379 DEG C.
Titanate esters modified kaolin addition is the aqueous polyurethane coating of 18%, after the chilled brittle failure of dry coating,
The plane of disruption is analyzed by scanned Electronic Speculum, and result is shown in Fig. 1.From left hand view in Fig. 1, through modification
Kaolin dispersion in aqueous polyurethane glued membrane is preferable, does not has a biggest gathering, and the enlarged drawing on right side
Furthermore, it can be seen that modified kaolin has the gathering of lower degree in glued membrane, the lamella of modified kaolin is inlayed
In polyurethane matrix, two-phase interface obscures, and this is owing to Kaolin is with active group, it is simple to coupling agent
As bridge, connect kaolin particle and polyurethane chain, strengthen two-phase interface adhesive force.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The industry
Skilled person will appreciate that, the present invention is not restricted to the described embodiments, in above-described embodiment and description
The principle that the present invention is simply described described, without departing from the spirit and scope of the present invention, the present invention
Also having various changes and modifications, these changes and improvements both fall within scope of the claimed invention.This
The claimed scope of invention is defined by appending claims and equivalent thereof.
Claims (6)
1. the preparation method of the aqueous polyurethane coating with modified kaolin as filler, it is characterised in that:
Comprise the following steps:
(1) by without calcining 8～12g Kaolin, 0.12～0.15g titanate coupling agent be scattered in 15～
In 20ml dehydrated alcohol, grind 30～60min, dry and reclaim ethanol, prepare hydrophilic modifying Kaolin；
(2) by 78～85g aqueous polyurethanes, 15～21g modified kaolin, 0.5g defoamer and 0.5～
1.5g thickening agent mixes, and ball milling disperses 30 60min, obtains the poly-ammonia of the aqueous with modified kaolin as filler
Ester paint.
The system of a kind of aqueous polyurethane coating with modified kaolin as filler the most according to claim 1
Preparation Method, it is characterised in that: the described aqueous polyurethane coating with modified kaolin as filler, its glued membrane
Hot strength is 15～24MPa, elongation at break be 412～448%, hardness 64～82 Shao A, water absorption rate
1.3～1.82%, maximum heat decomposition temperature 359～379 DEG C.
The system of a kind of aqueous polyurethane coating with modified kaolin as filler the most according to claim 1
Preparation Method, it is characterised in that: described titanate coupling agent is double (dioctylphyrophosphoric acid acyloxy) ethylene titaniums
Acid esters.
The system of a kind of aqueous polyurethane coating with modified kaolin as filler the most according to claim 1
Preparation Method, it is characterised in that: described aqueous polyurethane be water-based aliphaic polyurethane, aromatic waterborne gather
One or both in urethane, solid content is 30～55%, emulsion viscosity 30～100mPas；Particle diameter distribution 60～
200nm。
The system of a kind of aqueous polyurethane coating with modified kaolin as filler the most according to claim 1
Preparation Method, it is characterised in that: described defoamer is one or both in organosilicon, vegetable oil defoamer.
The system of a kind of aqueous polyurethane coating with modified kaolin as filler the most according to claim 1
Preparation Method, it is characterised in that: described thickening agent is organobentonite, butyl acetate cellulose, nonionic
One or more mixing in aqueous polyurethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610640316.6A CN106010202A (en) | 2016-08-05 | 2016-08-05 | Preparation method of aqueous polyurethane coating with modified kaolin as filler |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610640316.6A CN106010202A (en) | 2016-08-05 | 2016-08-05 | Preparation method of aqueous polyurethane coating with modified kaolin as filler |
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| CN201610640316.6A Pending CN106010202A (en) | 2016-08-05 | 2016-08-05 | Preparation method of aqueous polyurethane coating with modified kaolin as filler |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943220A (en) * | 2019-03-28 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of aqueous leather coating of wear-resisting scratch resistance and preparation method thereof |
| CN110818439A (en) * | 2019-09-09 | 2020-02-21 | 三河市纳诺科斯机电产品制造有限公司 | Method for preparing building ceramsite by using building garbage |
| CN111961355A (en) * | 2020-08-17 | 2020-11-20 | 西南石油大学 | Polymer-coated vanadium-titanium waste residue nano particle and preparation method thereof |
| CN114940735A (en) * | 2021-06-18 | 2022-08-26 | 佛山市三水联美化工有限公司 | High-water-solubility PU resin and preparation method thereof |
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| CN104059516A (en) * | 2014-07-09 | 2014-09-24 | 佛山市世冠化工科技有限公司 | Waterborne polyurethane wood solid color paint |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943220A (en) * | 2019-03-28 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of aqueous leather coating of wear-resisting scratch resistance and preparation method thereof |
| CN110818439A (en) * | 2019-09-09 | 2020-02-21 | 三河市纳诺科斯机电产品制造有限公司 | Method for preparing building ceramsite by using building garbage |
| CN111961355A (en) * | 2020-08-17 | 2020-11-20 | 西南石油大学 | Polymer-coated vanadium-titanium waste residue nano particle and preparation method thereof |
| CN111961355B (en) * | 2020-08-17 | 2021-05-04 | 西南石油大学 | Polymer-coated vanadium-titanium waste residue nano particle and preparation method thereof |
| CN114940735A (en) * | 2021-06-18 | 2022-08-26 | 佛山市三水联美化工有限公司 | High-water-solubility PU resin and preparation method thereof |
| CN114940735B (en) * | 2021-06-18 | 2023-09-15 | 佛山市三水联美化工有限公司 | High-solubility water-based PU resin and preparation method thereof |
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