CN109207039A - A kind of fluorine richness asparagus fern carbamide paint and preparation method thereof - Google Patents
A kind of fluorine richness asparagus fern carbamide paint and preparation method thereof Download PDFInfo
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- CN109207039A CN109207039A CN201811037228.2A CN201811037228A CN109207039A CN 109207039 A CN109207039 A CN 109207039A CN 201811037228 A CN201811037228 A CN 201811037228A CN 109207039 A CN109207039 A CN 109207039A
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- component
- agent
- fluorine
- asparagus fern
- fluorine richness
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Classifications
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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
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3831—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
Abstract
The invention discloses a kind of fluorine richness asparagus fern carbamide paints and preparation method thereof, are related to synthetic paint technical field.The advantages of present invention is by creatively combining asparagus fern polyureas and fluorocarbon coating, the coating that can be applied to wind electricity blade prepared with the fluorine-containing polyaspartic ester resin of fluorine richness, glass transition temperature can be significantly improved, improve the high temperature resistance of paint film, it further increases ageing-resistant under high temperature, anti- loss of gloss, the performances such as fastness, coating surface reduces water contact angle simultaneously, reduce wetting and erosion of the water to paint film, the resistance to water improved, when in the environment of wind electricity blade running on low temperature and high relative humidity, improves the ability of anti-ice cover.
Description
Technical field
The present invention relates to synthetic paint technical field, a kind of fluorine richness asparagus fern carbamide paint and its preparation side are referred in particular to
Method.
Background technique
Wind-driven power generation blade coating with Chinese clean energy resource specific gravity improve and scale constantly expands, because of wind electricity blade whole day
It waits, is used from summer high temperature to winter low temperature and under the various weather operating conditions of wind sand sleet various for a long time, while wind-powered electricity generation leaf
The length of piece reaches 60-80 meters, and the linear velocity in operating is up to 60-80 metre per second (m/s), dust, wind under this high speed in air
Sand, raindrop, ice and snow can all cause serious abrasion to wind electricity blade.The economic benefit of wind power generating set is directly by stable operation
Time and shutdown maintenance frequency directly affect, therefore have high protective performance requirement to wind-driven power generation blade coating, such as to base
The good adhesive force of material, resistance to weathering, -40 DEG C of low-temperature extensions, 3000h aging, the wet circulation of cold-hot, resistance to condensation etc..Conventional wind
Electric blade coating uses polyurethane system, and there are ageing-resistant performance deficiency, the high disadvantages of VOC emission；Polyaspartic ester is poly-
The wind-driven power generation blade coating height of urea system consolidates low VOC, and the feature of environmental protection is good, and low temperature flexibility is excellent, and ageing-resistant and resistance to weathering, which is able to satisfy, to be wanted
It asks, but water contact angle is lower, is difficult to avoid that as other systems and causes icing in the rain and snow weather of low temperature and high relative humidity.Also it adopts
Icing is solved the problems, such as with fluorine carbon system, is had excellent weather resistance simultaneously, but it is poor in the presence of repairing and recoating performance, and rigidity is too strong and low
Temperature flexibility and the lower problem of resistance to weathering performance.
Summary of the invention
The technical problems to be solved by the present invention are: how to improve the weatherability of coating, allow to be applied to well
On wind electricity blade.
In order to solve the above-mentioned technical problem, the invention discloses a kind of fluorine richness asparagus fern carbamide paints, by weight, packet
The component A and B component remixed when use is included, is formed are as follows:
Component A
B component
20~200 parts by weight of curing agent；
A when use, B component mixed weight ratio be 5:1~1:2.
The component A and B component remixed when further, by weight, including using, composition are as follows: component A
B component
25 parts by weight of curing agent.
A when use, B component mixed weight ratio be 4:1.
Further, the corresponding structural formula of the fluorine-containing polyaspartic ester resin are as follows:
In formula, R is aliphatic group.
Further, it counts by molar, the composition of raw materials composition of the fluorine-containing polyaspartic ester resins synthesis are as follows:
Further, the titanium dioxide selects rutile type titanium white；The dispersing agent selects the big of high-solid-content paint
Dispersal agent molecule.
Further, the thixotropic agent selects one of gas silicon class, polyamide wax class, polyureas thixotropic agent or a variety of.
Further, the levelling agent selects polyurethanes or fluorine richness class levelling agent；The coupling agent selects silane even
Join agent.
Further, the curing agent select HDI trimer, IPDI tripolymer, HDI prepolymer, in IPDI prepolymer
It is one or more.
Further, the NCO% of the curing agent is 3.5%~24%.
In addition, a kind of preparation method of fluorine richness asparagus fern carbamide paint is also disclosed, specifically: press the parts by weight
Into fluorine-containing polyaspartic ester resin be added titanium dioxide, barium sulfate, toner, dispersing agent, anti-settling agent, defoaming agent, levelling agent,
Coupling agent, ultraviolet absorbing agent stir evenly, as component A；Use the curing agent of the parts by weight as B component；When using
A, B component are stirred evenly to obtain the final product.
The advantages of by creatively utilizing asparagus fern polyureas and fluorocarbon coating, with the fluorine-containing polyaspartic ester of fluorine richness
The coating that can be applied to wind electricity blade of resin preparation, can significantly improve glass transition temperature, improve the heat-resisting quantity of paint film
Can, further increasing ageing-resistant under high temperature, anti-loss of gloss, the performances such as fastness, while coating surface reduces water contact angle, reduces
Wetting and erosion of the water to paint film, the resistance to water of raising when in the environment of wind electricity blade running on low temperature and high relative humidity, improve
The ability of anti-ice cover.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained in detail below in conjunction with embodiment.
A kind of fluorine richness asparagus fern carbamide paint, by weight, the component A and B component remixed when including using, composition
Are as follows:
Component A
B component
20~200 parts by weight of curing agent；
A when use, B component mixed weight ratio be 5:1~1:2, it also may be preferable for be 4:1.
Preferably, the corresponding structural formula of the fluorine-containing polyaspartic ester resin are as follows:
In formula, R is aliphatic group.
And it counts by molar, the composition of raw materials composition of the fluorine-containing polyaspartic ester resins synthesis are as follows:
Preferably, the polymerization inhibitor be one of p-hydroxyanisole, phenthazine, hydroquinone or a variety of, it is described to tie up
Sour agent is one of pyridine, triethylamine, potassium carbonate or a variety of, and the aliphatic group diamine is 4,4 '-diamino, two hexamethylene
Methylmethane, 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane, isophorone diamine, 1,6- hexamethylene diamine, 3- methyl-1,
5- pentanediamine, 1- methyl -2,4- cyclohexanediamine, 1,3- hexamethylene dimethylamine, 1,2- cyclohexane diamine, 1,3- cyclohexane diamine, 1,
One of 4- cyclohexane diamine, 1,3- ring pentanediamine, aminomethyl cyclopentamine, adjacent diamines methyl cyclopentane are a variety of.This is fluorine-containing
The corresponding synthetic method of polyaspartic ester resin are as follows: firstly, according to the composition of raw materials form, by fumaryl chloride,
Trifluoroethanol, polymerization inhibitor, acid binding agent uniformly mix, and keep the temperature 2~4 hours at 50~100 DEG C, and preferably isothermal holding temperature is 70
DEG C, the isothermal holding time is 3h.Then, by products therefrom water-washing desalting, rectification and purification, to obtain fumaric acid -1,1 ' -
Two (2,2,2- trifluoroethyl) esters.Finally, by (2,2, the 2- trifluoroethyl) ester of fumaric acid -1,1 '-two and aliphatic group two
First amine mixing keeps the temperature 12~72h at 60~90 DEG C, and preferably holding temperature is 70 DEG C, soaking time 48h, to be contained
Fluorine polyaspartic ester resin.
Preferably, the titanium dioxide selects rutile type titanium white, and oil absorption is low, and good to disperse, covering power is good, weatherability
It is good, high solid content and low viscosity and excellent ageing-resistant performance are provided for paint film.The dispersing agent selects big point of high-solid-content paint
Sub- dispersing agent, viscosity reducing effect and dispersion effect are good.The thixotropic agent selects gas silicon class, polyamide wax class, polyureas thixotropic agent
One of or it is a variety of, guarantee enough anti-settling and resist sagging performances.The levelling agent selects polyurethanes or fluorine richness
Class levelling agent, it is helpful to paint film levelling and take into account good overcoating performance.The coupling agent selects silane coupling agent, Ke Yizeng
Reinforcing body content reduces VOC, while improving the adhesive force to substrate.Paint film anti-ultraviolet ageing performance can be improved in ultraviolet absorber.
The curing agent selects one of HDI trimer, IPDI tripolymer, HDI prepolymer, IPDI prepolymer or a variety of.It is described solid
The NCO% of agent is 3.5%~24%.
In addition, a kind of preparation method of the fluorine richness asparagus fern carbamide paint, specifically: gather by the parts by weight to fluorine-containing
In aspartate resin be added titanium dioxide, barium sulfate, toner, dispersing agent, anti-settling agent, defoaming agent, levelling agent, coupling agent,
Ultraviolet absorbing agent stirs evenly, as component A；Use the curing agent of the parts by weight as B component；By A, B group when using
Divide and stir evenly to obtain the final product.
In addition, enumerating part typical case's specific example again below.
Embodiment 1
A kind of fluorine richness asparagus fern carbamide paint, specifically includes following component:
Component A
B component:
20 parts by weight of hexamethylene diisocyanate trimer；
80 parts by weight of dimerisation ispohorone diisolyanate body；
B component NCO% is 10.2%.
By component A and B component, proportionally 100:56 is uniformly mixed construction.
Meanwhile wherein used fluorine-containing polyaspartic ester resin, resin raw material needed for synthesizing can be packet
Include following components:
Maleic chloride, trifluoroethanol, p-hydroxybenzene ether, pyridine is negated to be mixed and heated in 1000ml four-hole boiling flask
3 hours are kept the temperature to 70 DEG C.Product water-washing desalting, last rectification and purification obtain (2,2, the 2- trifluoro second of fumaric acid -1,1 '-two
Base) ester.Take fumaric acid -1 353g, 4,4 '-diaminocyclohexyl first of 1 '-two (2,2,2- trifluoroethyl) ester and 110g
Alkane mixes in 500ml four-hole boiling flask, and the aspartate containing fluorine richness for obtaining that molecular weight is 772 for 48 hours is kept the temperature at 80 DEG C
Naval stores.Its key reaction formula are as follows:
Embodiment 2
A kind of fluorine richness asparagus fern carbamide paint, the coating include following component:
Component A
B component:
100 parts by weight of hexamethylene diisocyanate trimer；
B component NCO% is 23%.
By component A and B component, proportionally 5:1 is uniformly mixed construction.
Fluorine-containing polyaspartic ester resin used in meanwhile, composition of raw materials needed for synthesizing are as follows:
Maleic chloride, trifluoroethanol, p-hydroxybenzene ether, pyridine is negated to be mixed and heated in 1000ml four-hole boiling flask
3 hours are kept the temperature to 60 DEG C.Product water-washing desalting, last rectification and purification obtain (2,2, the 2- trifluoro second of fumaric acid -1,1 '-two
Base) ester.Take fumaric acid -1 353g, 1 '-two (2,2,2- trifluoroethyl) ester and 4,4 '-diamino-dicyclohexyl methanes and 3,
3 '-dimethyl -4,4 '-diamino-dicyclohexyl methanes mix in 500ml four-hole boiling flask, keep the temperature 60 hours at 70 DEG C and are divided
The product of aspartate containing fluorine richness that son amount is 791.
Embodiment 3
A kind of fluorine richness asparagus fern carbamide paint, the coating include following component
Component A
B component:
100 parts by weight of hexamethylene diisocyanate trimer；
B component NCO% is 23.5%.
By component A and B component, proportionally 1:0.31 is uniformly mixed construction.
Meanwhile used fluorine-containing polyaspartic ester resin, the composition of raw materials component of synthesis are as follows:
Maleic chloride, trifluoroethanol, p-hydroxybenzene ether, triethylamine is negated to mix and add in 1000ml four-hole boiling flask
Heat keeps the temperature 4 hours to 50 DEG C.Product water-washing desalting, last rectification and purification obtain 1,1 '-two (2,2,2- trifluoros of fumaric acid-
Ethyl) ester.Fumaric acid -1 353g, 1 '-two (2,2,2- trifluoroethyl) ester and isophorone diamine is taken to burn at tetra- mouthfuls of 500ml
It is mixed in bottle, the product of aspartate containing fluorine richness for obtaining that molecular weight is 732 for 30 hours is kept the temperature at 90 DEG C.
The A of above embodiment, B component are uniformly mixed, prepare the paint film of 60-200um thickness, and with similar commercially available production
Product compare, test result is as follows table 1.
Table 1
The present invention is by the improvement of formulation for coating material, and modified fluorine-containing poly- according to aspartate resin and elasticity of collocation
The isocyanates of urethane type prepares a kind of high performance coating that can be used for wind electricity blade.The present invention uses high-solid lower-viscosity
Fluorine-containing polyaspartic ester resin is used as curing agent, cooperates excellent as matrix resin, elastic cured dose of same high-solid lower-viscosity
The good dispersing agent of choosing drop viscosity effect, the pigments and fillers of low oil absorption ferric high durable, manufactured coating application can meet 250g/L green
The requirement of coating is without adding solvent, good environmental protection.Coating is good to glass steel substrate adhesive force.With conventional fluorine carbon wind electricity blade
Coating is compared, and paint film low temperature flexibility is good, and disposable thick painting may be implemented；With conventional asparagus fern polyureas wind-driven power generation blade coating phase
Than paint film high-temperature stability is good, and weatherability is more excellent, and anti-ice cover performance is good.Applied to wind electricity blade coating protection, it is possible to reduce apply
The VOC emission of dress process reduces the discharge pressure of construction enterprises and improves the working environment of worker；For wind-powered electricity generation operator
Can it is permanently effective protection wind electricity blade stable operation, it is not easy to allow blade that aging and mill occur during running at high speed
Erosion avoids reducing wind electricity blade because wind electricity blade abrasion causes the aerodynamic reduction for changing and leading to generating efficiency and existing
The risk of southern low temperature and high relative humidity season blade surface icing, reduces the number of maintenance shut-downs, improve project economic income rate and
Investment repayment.Attention of the China for clean energy resource causes wind-driven generator installed capacity high speed to be incremented by, starts every year since 2010
Adding new capacity is all at 20,000,000 kilowatts or so, the market capacity and steady demand of wind-driven power generation blade coating, in addition existing installation
Capacity is up to 1.88 hundred million kilowatts, and the blade maintenance coating of old blower also has huge market, therefore the product has good market
Prospect.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent transformation made by bright description is applied directly or indirectly in other relevant technical fields, and is similarly included in
In scope of patent protection of the invention.
Claims (10)
1. a kind of fluorine richness asparagus fern carbamide paint, which is characterized in that by weight, the component A and B remixed when including using
Component, composition are as follows:
Component A
B component
20~200 parts by weight of curing agent；
A when use, B component mixed weight ratio be 5:1~1:2.
2. fluorine richness asparagus fern carbamide paint as described in claim 1, which is characterized in that by weight, including when using again
Mixed component A and B component, composition are as follows:
Component A
B component
25 parts by weight of curing agent；
A when use, B component mixed weight ratio be 4:1.
3. fluorine richness asparagus fern carbamide paint as claimed in claim 1 or 2, which is characterized in that the fluorine-containing poly-aspartic-acid
The corresponding structural formula of ester resin are as follows:
In formula, R is aliphatic group.
4. fluorine richness asparagus fern carbamide paint as claimed in claim 3, which is characterized in that count by molar, the fluorine-containing poly- day
The composition of raw materials of L-aminobutanedioic acid ester resins synthesis forms are as follows:
5. fluorine richness asparagus fern carbamide paint as claimed in claim 1 or 2, which is characterized in that the titanium dioxide selects rutile
Type titanium dioxide；The dispersing agent selects the macromolcular dispersant of high-solid-content paint.
6. fluorine richness asparagus fern carbamide paint as claimed in claim 1 or 2, which is characterized in that the thixotropic agent selection gas silicon class,
One of polyamide wax class, polyureas thixotropic agent are a variety of.
7. fluorine richness asparagus fern carbamide paint as claimed in claim 1 or 2, which is characterized in that the levelling agent selects polyurethane
Class or fluorine richness class levelling agent；The coupling agent selects silane coupling agent.
8. fluorine richness asparagus fern carbamide paint as claimed in claim 1 or 2, which is characterized in that the curing agent selects HDI trimerization
One of body, IPDI tripolymer, HDI prepolymer, IPDI prepolymer are a variety of.
9. fluorine richness asparagus fern carbamide paint as claimed in claim 8, which is characterized in that the NCO% of the curing agent is 3.5%
~24%.
10. the preparation method of fluorine richness asparagus fern carbamide paint as described in claim any one of 1-9, it is characterised in that: by described
Parts by weight be added into fluorine-containing polyaspartic ester resin titanium dioxide, barium sulfate, toner, dispersing agent, anti-settling agent, defoaming agent,
Levelling agent, coupling agent, ultraviolet absorbing agent stir evenly, as component A；Use the curing agent of the parts by weight as B component；In
A, B component are stirred evenly when use to obtain the final product.
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| CN201811037228.2A CN109207039B (en) | 2018-09-06 | 2018-09-06 | Fluorine modified asparagus polyurea coating and preparation method thereof |
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| CN201811037228.2A CN109207039B (en) | 2018-09-06 | 2018-09-06 | Fluorine modified asparagus polyurea coating and preparation method thereof |
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| CN110527370A (en) * | 2019-09-27 | 2019-12-03 | 大连科恩新材料发展有限公司 | A kind of polyurea modified fluorine carbon reflective heat-insulation paint and preparation method thereof |
| CN112812305A (en) * | 2020-12-30 | 2021-05-18 | 浙江艾特普科技有限公司 | Fluorine modified PAE resin, preparation method thereof and coating composition |
| CN114196304A (en) * | 2022-01-08 | 2022-03-18 | 深圳飞扬骏研新材料股份有限公司 | Solvent-free fluorine-modified polyaspartic acid ester multifunctional heat-insulating coating |
| CN114958269A (en) * | 2022-05-26 | 2022-08-30 | 万华化学集团股份有限公司 | Fluorine-silicon modified polyurea sealant with long service life and preparation method thereof |
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| CN114958269A (en) * | 2022-05-26 | 2022-08-30 | 万华化学集团股份有限公司 | Fluorine-silicon modified polyurea sealant with long service life and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN109207039B (en) | 2021-01-05 |
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