CN109608617A - Aqueous anti-stone hits blocked polyisocyanates curing agent and preparation method thereof, water paint - Google Patents
Aqueous anti-stone hits blocked polyisocyanates curing agent and preparation method thereof, water paint Download PDFInfo
- Publication number
- CN109608617A CN109608617A CN201811530053.9A CN201811530053A CN109608617A CN 109608617 A CN109608617 A CN 109608617A CN 201811530053 A CN201811530053 A CN 201811530053A CN 109608617 A CN109608617 A CN 109608617A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- alcohol
- hits
- stone
- blocked polyisocyanates
- 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.)
- Pending
Links
Classifications
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The aqueous anti-stone of one kind hits blocked polyisocyanates curing agent and preparation method thereof, water paint.The aqueous anti-stone hits blocked polyisocyanates curing agent, contains following raw material: polyisocyanate compound, hydrophilic chain alcohol, active methylene group class sealer, cosolvent, the alkaline metal salt of alcohol, neutralizer；Wherein, NCO mole should be greater than the mole of total active hydrogen in the polyisocyanate compound.The invention also includes aqueous anti-stones to hit the preparation method of blocked polyisocyanates curing agent, water paint.Curing agent of the invention can be improved film crosslink density, and then be lifted at the anti-stoning energy of the automobile floating coat under the conditions of low film thickness.
Description
Technical field
The present invention relates to anti-stones to hit polyisocyanate curing agent, and in particular to the aqueous anti-stone of one kind hits blocked polyisocyanates
Curing agent and preparation method thereof, water paint.
Background technique
With advances in technology and the development of basic means of transportation, automobile is more more and more universal, and road conditions also become increasingly complex, this
While bringing great convenience to masses, also to the surface covering of automobile, more stringent requirements are proposed.Automobile is as important family
The outer vehicles can be potentially encountered the shock of various types sandstone in high-speed cruising.Therefore, it is necessary to promote the resistance to of automotive coatings
Hitting property of stone hits the injury caused by automotive coatings to reduce sandstone, to protect automobile.
Currently, since floating coat generally uses Amino-Polyester Baking Paint, design is thick in traditional solvent based coating system
Degree generally can achieve its anti-stone and hit purpose in 40um or so.It is right as current various concerned countries environmental regulations are put into effect in succession
The VOCs limitation that the production of car paint and coating process generate is increasingly stringenter, higher and higher to formulation for coating material technical requirements,
These solvent based coating kinds apply film thickness, are gradually eliminated since VOC content is exceeded.In recent years, new coating system is more
More is designed around how to reduce volatile organic matter (VOC), and the thickness of still film layer, which has no, to have clear improvement.
Exempt to grind in high temperature and apply and its preparation side for example, prior art CN107163799A discloses a kind of striking waters property of Gao Naishi
Method, the striking waters property of Gao Naishi exempt to grind the primary raw material that applies in high temperature include: by weight 30-50 parts of aqueous polyester resin,
10-20 parts of organic silicon modified aqueous polyester emulsion, 5-15 parts of water-compatible amino resin, 0.1-1 parts of diethanol amine, aqueous promoter
0.5-3 parts, 10-15 parts of titanium dioxide, 10-15 parts of ultrafine mica powder, 5-10 parts of Graphene powder, 2-5 parts of Folium Nelumbinis essenc, deionized water
10-12 parts.The invention utilizes the flexibility of aqueous polyester resin and organic silicon modified aqueous polyester, and the piece using graphene
Shape, elastic construction greatly provide the anti-stoning energy of paint film, but in the anti-stoning energy for reaching needs, the film of coating
Thickness reaches 40um, and production cost is also higher.
CN102977752A is disclosed to be applied and preparation method thereof in a kind of aqueous automobile, is applied in the aqueous automobile by following
The group of parts by weight is grouped as: polyester resin A10~30 part, 0.5~3 part of dispersant A, defoaming agent A0.5~2 part,
0~0.5 part of carbon black, 10~30 parts of titanium dioxide, 0~3 part of talcum powder, 0.5~2 part of styrax, defoaming agent
B1~3 part, polyester resin B10~30 part, 2~6 parts of acrylic emulsion, 1~5 part of bisphenol-A polyethers,
First fourth mixes 2~10 parts of etherified amino resins, 0.5~2 part of acid catalyst, 0.1~1 part of dispersant B, ground profit
0.1~1 part of humectant, 0.2~2 part of levelling agent, 1~10 part of Amino resin, anti-shrinkage cavity auxiliary agent 0.1
~1 part, 0.2~0.5 part of organic amine, 5~20 parts of deionized water.The invention using the flexibility of polyester resin come
Realize anti-stoning, and anti-stoning energy required for reaching corresponding, then film film thickness must be increased, thus then be will lead into
This increase, energy consumption increase.
CN106987201A discloses a kind of aqueous polyurethane floating coating and preparation method thereof, the aqueous polyurethane floating coating
Including following component according to the mass fraction: 15-30 parts of water-based hydroxyl acrylic acid dispersion, anion pp acid dispersion
10-25 parts, aqueous aliphatic isocyanates 5-15 parts, 15-55 parts of pigments and fillers, 6-19 parts of auxiliary agent, 10-30 parts of deionized water.It should
Invention solves the automobile-used floating coating in China still based on solvent type, and a large amount of volatility is contained in the floating coating of solvent-based system
Organic matter (VOC), the extremely serious technical problem of the pollution to environment, has reached using deionized water as solvent, contained has
Malicious harmful substance significantly reduces, but film thickness reaches 80 μm or more, substantially increases production cost.
To sum up, from the point of view of environmental protection, the various aspects such as national and major automobile vendor, which are desirable in, meets film
Various aspects of performance under the premise of, as far as possible reduce coating thickness, while by the design film thickness of middle painting be reduced to 25um a left side
The right side to reduce VOCs discharge, while reducing energy consumption, reduces cost, realize energy-saving purpose, this applies vehicle surfaces
More stringent requirements are proposed for layer.It would therefore be highly desirable to which developing the new aqueous anti-stone of one kind hits blocked isocyanate curing agent, applied to improve
Film crosslink density is lifted at the anti-stoning energy of the automobile floating coat under the conditions of low film thickness with this.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of nothing to overcome the above problem of the existing technology
Aromatic hydrocarbons, ether solvent, no volatile NCO, low VOC emission, and can effectively promote the watersoluble closed of thin coating film anti-stoning
Polyisocyanate curing agent.
The present invention is further the technical problem to be solved is that, providing the aqueous anti-stone of one kind hits blocked polyisocyanates solidification
The preparation method of agent.
The present invention is further the technical problem to be solved is that, provide a kind of anti-stone aqueous as made from above-mentioned preparation method
Hit blocked polyisocyanates curing agent.
The present invention is further the technical problem to be solved is that, provide a kind of water paint of anti-stoning.
The technical solution used to solve the technical problems of the present invention is that a kind of aqueous anti-stone hits blocked polyisocyanates solidification
Agent, the curing agent contain following raw material: polyisocyanate compound, hydrophilic chain alcohol, active methylene group class sealer, cosolvent,
Alkaline metal salt, the neutralizer of alcohol；The polyisocyanate compound is selected from aliphatic isocyanates tripolymer, alicyclic isocyanide
At least one of acid esters tripolymer, aromatic isocyanate tripolymer, it is 300-2000 that the hydrophilic chain alcohol, which is selected from molecular weight,
At least one of polyglycol ether monohydric alcohol；NCO mole should be greater than total active hydrogen (hydroxyl in the polyisocyanate compound
Base and active methylene group sealer) mole.
In the present invention, due in polyisocyanate compound NCO mole be greater than total active hydrogen (including hydroxyl and active
Active hydrogen in methylene sealer) mole so that first active hydrogen (methylene) in active methylene group class sealer
When having completely consumed, there are still the NCO being partially not closed out in system, and the unclosed NCO in the part continues and active methylene group
Second hydrogen (methine) of class sealer carries out capping, completely encloses until by all NCO, is formed a kind of as follows
Special elastic structure:
Wherein, X is polyisocyanate compound main chain section, and Y is the functional group of reactable resin, and R is active methylene group class envelope
The alkoxy substituted of agent is closed, Z is acetyl group or ester group.
The elastic construction can occur anti-with the resin of the active group such as amino resins, polyester resin in formulation for coating material
The face type or three-dimensional-structure that should be formed, to improve the crosslink density of film, and when film can be delayed to hit or hit by stone
Energy release, and then promote the anti-stoning energy of coating of film under the conditions of low film thickness.
In the present invention, the crosslink density that aqueous anti-stone hits blocked polyisocyanates curing agent is by polyisocyanates chemical combination
First remaining NCO mole of active hydrogen (methylene) that object has completely consumed active methylene group class sealer is determined.
Further, on the basis of the total weight of polyisocyanate curing agent, polyisocyanate compound 35-60 weight %, parent
Water chain alcohol 5-15 weight %, active methylene group class sealer 5-25 weight %, cosolvent 10-30 weight %, alcohol alkaline metal salt
0.3-0.7 weight %, neutralizer 0.1-0.5 weight %.
Further, the hydrophilic chain alcohol is selected from the poly glycol monomethyl ether that molecular weight is 300-1000.
Further, the polyisocyanate compound is isophorone diisocyanate trimer, two isocyanide of hexa-methylene
At least one of acid esters tripolymer.
Further, the active methylene group class sealer is selected from the active methylene with structure shown in formula (I) and formula (II)
At least one of base class sealer,
R1, R2, R3Respectively stand alone as C1-C6Alkoxy.
For example, the active methylene group class sealer can select ethyl acetoacetate, isopropyl acetoacetate, malonic acid two
Methyl esters, diethyl malonate, at least one of Diisopropyl malonate and isopropylidene malonate.
Further, the cosolvent is C1-C10At least one of saturation unitary fatty alkyl alcohol；The alkali metal of the alcohol
Salt is at least one of potassium tert-butoxide, sodium methoxide, methanol solution of sodium methylate and alcohol sodium alcohol solution；The neutralizer is
Phosphoric acid and/or sulfuric acid.
The present invention further solve its technical problem the technical solution adopted is that, a kind of aqueous anti-stone hits closing polyisocyanic acid
The preparation method of ester curing agent, comprising the following steps:
(1) hydrophilic chain alcohol and polyisocyanate compound are subjected to hydrophilic modifying, obtain carbamate prepolymer；
(2) alkaline metal salt of active methylene group class sealer and alcohol is pre-dispersed, it obtains active methylene group class sealer and divides in advance
Granular media can preferably catalytic synthesis be carried out through pre-dispersed base-metal salt；
(3) by the carbamate prepolymer and the active methylene group class sealer predispersion under the conditions of 40-60 DEG C
Sealing end 0.5-5 h for the first time is carried out, with pure polyisocyanates content meter, the mass fraction of the residual volume of NCO is 3.79-26.51%
(, second of sealing end 8-12 h, mass fraction≤0.4% of the residual volume of NCO are then carried out under the conditions of 70-90 DEG C；
(4) neutralizer is added in step (3) products therefrom and adjusts pH value, cosolvent is then added and adjusts solid content, filters, system
It obtains aqueous anti-stone and hits blocked polyisocyanates curing agent.
The reaction formula of preparation process of the present invention, as shown in formula (III):
Formula (III)
In the present invention, since there are two active hydrogens for active methylene group class sealer, first active hydrogen is in closing, energy barrier
It is lower, therefore reaction temperature is low, the reaction time is short；When second active hydrogen closing NCO, since steric hindrance is larger, it is more difficult to reaction, therefore
And required temperature is high, the end capping reaction time is longer.
It further, further include that hydrophilic chain dehydration of alcohols is controlled into hydrophilic chain alcohol before the hydrophilic modifying in step (1)
Water content is 0.01-0.1 weight %.
Further, it is 700-760mmHg that the condition of the dehydration, which includes: negative pressure, and temperature is 80-105 DEG C, and the time is
0.5-8h。
Further, in step (1), the temperature of the hydrophilic modifying is 40-90 DEG C.
Further, in step (4), the solid content is 70-90 weight %, and the pH value is 7-10.
The present invention further solve its technical problem the technical solution adopted is that, it is a kind of according to preparation method described above
Aqueous anti-stone obtained hits blocked polyisocyanates curing agent.
The present invention further solve its technical problem the technical solution adopted is that, a kind of water paint, the water paint packet
Containing non-ion aqueous blocked polyisocyanates curing agent described above.
Compared with prior art, the invention has the following advantages:
(1) without aromatic hydrocarbons, ether solvent, no volatile NCO, low VOC emission in curing agent of the invention；
(2) in curative systems of the invention there are special elastic construction, film can effectively be promoted under the conditions of low film thickness
The anti-stoning energy of coating；
(3) curing agent synthesis technology of the invention is simple.
Specific embodiment
The present invention will be described in detail by way of examples below.In following embodiment,
NCO residual volume is measured referring to " polymethylene multi-phenenyl isocyanate radical content measuring method " in GB12009.4-89.
Film crosslink density is measured by your a point rate of lid；Wherein, lid you divide rate test method: with clean iron plate from glass
The film being fully cured is scraped on plate, quality is referred to as m0, the film weighed up is placed in methanol/acetone (volume ratio 1:1), 60
DEG C reflux 6h, then by film be placed in 30 DEG C of thermostatic drying chambers it is dry for 24 hours, claim film quality m1。
Then cover your point rate=。
Gai Erfen rate is bigger, and film crosslink density is bigger.
Anti- stone hits grade and according to DIN EN ISO 20567-1 carries out resistance to stone and hit test method measuring.
In case of no particular description, raw materials used to be all made of commercial product.
It is each embodiment charge ratio table below, as shown in table 1.
Table 1
Embodiment 1
(1) hydrophilic chain alcohol (poly glycol monomethyl ether mpeg 3 00) is placed in four round flask, is inserted into thermometer, then opens
Open oil pump, decompression water removal (negative pressure 750mmHg, temperature are 99 DEG C, time 4h), terminal point control hydrophilic chain alcohol (poly- second two
Alcohol monomethyl ether mpeg 3 00) water content be 0.07%, be cooled to 40 DEG C.
(2) by dress reflux condensing tube, thermocouple, thermometer, nitrogen tube in above-mentioned four round flask, in stirring
Under, ethyl acetate, HDI trimer polyisocyanates is added, while being blown into nitrogen, disperses 15min, then heat to 95 DEG C, stop
It is only blown into nitrogen, 2h is reacted, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (potassium tert-butoxide) and active methylene group class sealer (ethyl acetoacetate and acetyl
Isopropyl acetate) it is pre-dispersed at room temperature, obtain malonic acid mixed ester.
(4) completely after completion of the reaction to the polyisocyanate compound of hydrophilic chain alcohol and isocyanurate structure, cooling drop
Temperature to 30 DEG C, by the carbamate prepolymer and the active methylene group class sealer predispersion under the conditions of 40 DEG C into
Row blocks 5 h for the first time, and second of sealing end 8h is then carried out under the conditions of 90 DEG C, and until measuring NCO≤0.4%, sealing end terminates,
Stop reaction.
(5) phosphoric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Isopropanol is added, adjusts
Whole amount of solid content is 70%, and adjustment pH value is 8.0, adds 400 mesh diatomite filtering and dischargings, aqueous anti-stone is made and hits polyisocyanic acid
Ester.
Embodiment 2
(1) hydrophilic chain alcohol (poly glycol monomethyl ether MPEG600) is placed in four round flask, is inserted into thermometer, then opens
Open oil pump, decompression water removal (negative pressure 760mmHg, temperature are 105 DEG C, time 3h), terminal point control hydrophilic chain alcohol (poly- second two
Alcohol monomethyl ether MPEG600) water content be 0.05%, be cooled to 40 DEG C.
(2) by dress reflux condensing tube, thermocouple, thermometer, nitrogen tube in above-mentioned four round flask, in stirring
Under, ethyl acetate, IPDI tripolymer polyisocyanates is added, while being blown into nitrogen, disperses 15min, then heat to 95 DEG C, stop
It is only blown into nitrogen, 1.5h is reacted, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (sodium methoxide) and active methylene group class sealer (dimethyl malenate and malonic acid
Diethylester) it is pre-dispersed at room temperature, obtain malonic acid mixed ester.
(4) completely after completion of the reaction to the polyisocyanate compound of hydrophilic chain alcohol and isocyanurate structure, cooling drop
Temperature to 30 DEG C, by the carbamate prepolymer and the active methylene group class sealer predispersion under the conditions of 50 DEG C into
Row blocks 3h for the first time, and second of sealing end 10h is then carried out under the conditions of 80 DEG C, and until measuring NCO≤0.4%, sealing end terminates,
Stop reaction.
(5) sulfuric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Methyl tert-butyl is added
Base methanol, adjustment amount of solid content are 80%, and adjustment pH value is 7.5, add 400 mesh diatomite filtering and dischargings, aqueous anti-stone is made and hits
Polyisocyanates.
Embodiment 3
(1) hydrophilic chain alcohol (poly glycol monomethyl ether MPEG1000) is placed in four round flask, is inserted into thermometer, then opens
Open oil pump, decompression water removal (negative pressure 755mmHg, temperature are 100 DEG C, time 3.5h), terminal point control hydrophilic chain alcohol (poly- second
Glycol monomethyl ether MPEG1000) water content be 0.06%, be cooled to 40 DEG C.
(2) by dress reflux condensing tube, thermocouple, thermometer, nitrogen tube in above-mentioned four round flask, in stirring
Under, ethyl acetate, HDI trimer polyisocyanates is added, while being blown into nitrogen, disperses 15min, then heat to 95 DEG C, stop
It is only blown into nitrogen, 2.5h is reacted, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (methanol solution of sodium methylate) and active methylene group class sealer (methyl acetoacetate
And Diisopropyl malonate) pre-dispersed at room temperature, obtain malonic acid mixed ester.
(4) completely after completion of the reaction to the polyisocyanate compound of hydrophilic chain alcohol and isocyanurate structure, cooling drop
Temperature to 30 DEG C, by the carbamate prepolymer and the active methylene group class sealer predispersion under the conditions of 60 DEG C into
Row blocks 0.5h for the first time, second of sealing end 12h is then carried out under the conditions of 90 DEG C, until measuring NCO≤0.4%, sealing end is tied
Beam stops reaction.
(5) sulfuric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Ten carbon alcohol are added, adjust
Whole amount of solid content is 90%, and adjustment pH value is 8.5, adds 400 mesh diatomite filtering and dischargings, aqueous anti-stone is made and hits polyisocyanic acid
Ester.
Embodiment 4
(1) hydrophilic chain alcohol (poly glycol monomethyl ether MPEG600, MPEG1000) is placed in four round flask, is inserted into temperature
Meter, later on oil pump, decompression water removal (negative pressure 750mmHg, temperature are 101 DEG C, time 4h), terminal point control hydrophilic chain
The water content of alcohol (poly glycol monomethyl ether MPEG600, MPEG1000) is 0.04%, is cooled to 40 DEG C.
(2) by dress reflux condensing tube, thermocouple, thermometer, nitrogen tube in above-mentioned four round flask, in stirring
Under, ethyl acetate, HDI trimer/IPDI tripolymer polyisocyanates is added, while being blown into nitrogen, disperses 15min, then rise
For temperature to 95 DEG C, stopping is blown into nitrogen, reacts 2h, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (alcohol sodium alcohol solution) and active methylene group class sealer (diethyl malonate/
Diisopropyl malonate) it is pre-dispersed at room temperature, obtain malonic acid mixed ester.
(4) completely after completion of the reaction to the polyisocyanate compound of hydrophilic chain alcohol and isocyanurate structure, cooling drop
Temperature to 30 DEG C, by the carbamate prepolymer and the active methylene group class sealer predispersion under the conditions of 50 DEG C into
Row blocks 3h for the first time, and second of sealing end 12h is then carried out under the conditions of 70 DEG C, and until measuring NCO≤0.4%, sealing end terminates,
Stop reaction.
(5) phosphoric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Methyl tert-butyl is added
Base methanol, adjustment amount of solid content are 70%, and adjustment pH value is 9.0, add 400 mesh diatomite filtering and dischargings, aqueous anti-stone is made and hits
Polyisocyanates.
Test case
It is as shown in table 2 according to formulation for coating material, aqueous anti-stone made from embodiment 1-4 is hit into blocked polyisocyanates curing agent and is prepared
At corresponding water paint 1-4, Cohan is created in contrast with the preparation of the watersoluble closed polyisocyanate curing agent of Baybond XL 7270
Coating carries out the relevant evaluation of coating performance parameter.
Table 2
Water paint 1-4 and comparison coating are made to the floating coat of different-thickness, using 508 Erichsen multiples impacts instrument, according to DIN
EN ISO 20567-1 standard carries out anti-stone and hits experiment test, and testing result is as shown in 3 tables.The appearance of film is had detected simultaneously
(GB/T 1743-79 (89)), adhesive force (HKSTM-2624), impact (GB1739-79), cup convex (GB/T 9753-2007), lead
Hardness (GB/T 1730-2007), water-fast (NES M0007 [2014] 57), wet-heat resisting (GB/T 1740-2007), acidproof
(GB/T1763), indices such as alkaline-resisting (GB/T1763), are able to satisfy performance requirement.
Table 3
It is tested from coating performance parameter it is found that creating the watersoluble closed polyisocyanate curing agent of Baybond XL 7270 with Cohan
It compares, embodiment 1-4 is made aqueous anti-stone and hits blocked polyisocyanates curing agent and can not influence appearance of film and items
While energy, crosslink density is bigger, is obviously improved the anti-stoning energy of film.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of aqueous anti-stone hits blocked polyisocyanates curing agent, which is characterized in that the curing agent contains following raw material: polyisocyanate
Cyanate esters, hydrophilic chain alcohol, active methylene group class sealer, cosolvent, the alkaline metal salt of alcohol, neutralizer；It is described more
Isocyanate compound is selected from aliphatic isocyanates tripolymer, alicyclic isocyanate tripolymer, aromatic isocyanate three
At least one of aggressiveness, the hydrophilic chain alcohol is at least one in the polyglycol ether monohydric alcohol that molecular weight is 300-2000
Kind, NCO mole should be greater than the mole of total active hydrogen in the polyisocyanate compound.
2. aqueous anti-stone according to claim 1 hits blocked polyisocyanates curing agent, which is characterized in that with polyisocyanic acid
On the basis of the total weight of ester curing agent, polyisocyanate compound 35-60 weight %, hydrophilic chain alcohol 5-15 weight %, active methylene
Base class sealer 5-25 weight %, cosolvent 10-30 weight %, alcohol alkaline metal salt 0.3-0.7 weight %, neutralizer 0.1-0.5
Weight %；
Preferably, the hydrophilic chain alcohol is selected from the poly glycol monomethyl ether that molecular weight is 300-1000.
3. aqueous anti-stone according to claim 1 or 2 hits blocked polyisocyanates curing agent, which is characterized in that described more
Isocyanate compound is isophorone diisocyanate trimer, at least one in hexamethylene diisocyanate trimer
Kind.
4. aqueous anti-stone according to claim 1 or 2 hits blocked polyisocyanates curing agent, which is characterized in that the work
Sprinkle methylene base class sealer is selected from the active methylene group class sealer with structure shown in formula (I) and formula (II) at least one
Kind,
R1, R2, R3 respectively stands alone as C1-C6Alkoxy.
5. aqueous anti-stone according to claim 1 or 2 hits blocked polyisocyanates curing agent, which is characterized in that described to help
Solvent is C1-C10At least one of saturation unitary fatty alkyl alcohol；The alkaline metal salt of the alcohol is potassium tert-butoxide, methanol
At least one of sodium, methanol solution of sodium methylate and alcohol sodium alcohol solution；The neutralizer is phosphoric acid and/or sulfuric acid.
6. the preparation side that aqueous anti-stone described in a kind of any one of claim 1-5 hits blocked polyisocyanates curing agent
Method, which comprises the following steps:
(1) hydrophilic chain alcohol and polyisocyanate compound are subjected to hydrophilic modifying, obtain carbamate prepolymer；
(2) alkaline metal salt of active methylene group class sealer and alcohol is pre-dispersed, it obtains active methylene group class sealer and divides in advance
Granular media；
(3) by the carbamate prepolymer and the active methylene group class sealer predispersion under the conditions of 40-60 DEG C
Sealing end 0.5-5 h for the first time is carried out, with pure polyisocyanates content meter, the residual volume of NCO is 3.79-26.51%, then in 70-
Second of sealing end 8-12 h, residual volume≤0.4% of NCO are carried out under the conditions of 90 DEG C；
(4) neutralizer is added in step (3) products therefrom and adjusts pH value, cosolvent is then added and adjusts solid content, filters, system
It obtains aqueous anti-stone and hits blocked polyisocyanates curing agent.
7. preparation method according to claim 6, which is characterized in that in step (1), before the hydrophilic modifying, also wrap
Including and hydrophilic chain dehydration of alcohols is controlled to the water content of hydrophilic chain alcohol is 0.01-0.1 weight %；
Preferably, it is 700-760mmHg that the condition of the dehydration, which includes: negative pressure, and temperature is 80-105 DEG C, time 0.5-
8h；
Preferably, in step (1), the temperature of the hydrophilic modifying is 40-90 DEG C.
8. preparation method according to claim 6 or 7, which is characterized in that in step (4), the solid content is 70-90 weight
% is measured, the pH value is 7-10.
9. aqueous anti-stone made from a kind of preparation method according to any one of claim 6-8 hits closing polyisocyanic acid
Ester curing agent.
10. a kind of water paint, which is characterized in that the water paint includes non-described in any one of claim 1-5 or 9
The watersoluble closed polyisocyanate curing agent of ionic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811530053.9A CN109608617A (en) | 2018-12-14 | 2018-12-14 | Aqueous anti-stone hits blocked polyisocyanates curing agent and preparation method thereof, water paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811530053.9A CN109608617A (en) | 2018-12-14 | 2018-12-14 | Aqueous anti-stone hits blocked polyisocyanates curing agent and preparation method thereof, water paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109608617A true CN109608617A (en) | 2019-04-12 |
Family
ID=66009320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811530053.9A Pending CN109608617A (en) | 2018-12-14 | 2018-12-14 | Aqueous anti-stone hits blocked polyisocyanates curing agent and preparation method thereof, water paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109608617A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396163A (en) * | 2019-08-26 | 2019-11-01 | 江苏华峰超纤材料有限公司 | The water cross-linking agent and its preparation method and application of amido-containing acid ester structure |
| CN110452362A (en) * | 2019-08-20 | 2019-11-15 | 湖南湘江关西涂料有限公司 | Watersoluble closed isocyanate curing agent and preparation method thereof, water paint |
| CN111303372A (en) * | 2019-10-30 | 2020-06-19 | 重庆绿涂腾科技有限公司 | Graphene oxide modified water-based closed isocyanate curing agent and preparation method thereof |
| CN112694598A (en) * | 2020-12-18 | 2021-04-23 | 江西瀚泰新材料科技有限公司 | Curing agent composition for water-based two-component coating |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10183060A (en) * | 1996-12-20 | 1998-07-07 | Bayer Ag | Cosolvent-free aqueous anionic polyurethane dispersion and use thereof as releasable coating |
| CN104334658A (en) * | 2012-05-24 | 2015-02-04 | 关西涂料株式会社 | Water-based coating composition, method for forming multi-layer coating film, and article having multi-layer coating film |
| CN104661763A (en) * | 2012-09-20 | 2015-05-27 | 关西涂料株式会社 | Method for forming multilayer coating film |
| CN104797350A (en) * | 2012-10-01 | 2015-07-22 | 关西涂料株式会社 | Process for forming multilayer coating film |
| CN105705597A (en) * | 2013-08-27 | 2016-06-22 | 关西涂料株式会社 | Water-based paint composition and painted article |
| CN107793544A (en) * | 2017-10-24 | 2018-03-13 | 佛山市精信汇明科技有限公司 | A kind of environment-friendly polyurethane curing agent and its preparation method and application |
-
2018
- 2018-12-14 CN CN201811530053.9A patent/CN109608617A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10183060A (en) * | 1996-12-20 | 1998-07-07 | Bayer Ag | Cosolvent-free aqueous anionic polyurethane dispersion and use thereof as releasable coating |
| CN104334658A (en) * | 2012-05-24 | 2015-02-04 | 关西涂料株式会社 | Water-based coating composition, method for forming multi-layer coating film, and article having multi-layer coating film |
| CN104661763A (en) * | 2012-09-20 | 2015-05-27 | 关西涂料株式会社 | Method for forming multilayer coating film |
| CN104797350A (en) * | 2012-10-01 | 2015-07-22 | 关西涂料株式会社 | Process for forming multilayer coating film |
| CN105705597A (en) * | 2013-08-27 | 2016-06-22 | 关西涂料株式会社 | Water-based paint composition and painted article |
| CN107793544A (en) * | 2017-10-24 | 2018-03-13 | 佛山市精信汇明科技有限公司 | A kind of environment-friendly polyurethane curing agent and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452362A (en) * | 2019-08-20 | 2019-11-15 | 湖南湘江关西涂料有限公司 | Watersoluble closed isocyanate curing agent and preparation method thereof, water paint |
| CN110396163A (en) * | 2019-08-26 | 2019-11-01 | 江苏华峰超纤材料有限公司 | The water cross-linking agent and its preparation method and application of amido-containing acid ester structure |
| CN111303372A (en) * | 2019-10-30 | 2020-06-19 | 重庆绿涂腾科技有限公司 | Graphene oxide modified water-based closed isocyanate curing agent and preparation method thereof |
| CN112694598A (en) * | 2020-12-18 | 2021-04-23 | 江西瀚泰新材料科技有限公司 | Curing agent composition for water-based two-component coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608617A (en) | Aqueous anti-stone hits blocked polyisocyanates curing agent and preparation method thereof, water paint | |
| CN109593182B (en) | Nonionic water-based blocked polyisocyanate curing agent, preparation method thereof and water-based paint | |
| CN109642099B (en) | Polyurethane coating compositions containing 1,1-di activated vinyl compounds and related coatings and methods | |
| EP1939232B1 (en) | Highly crosslinkable low-viscosity polyisocyanate composition and coating composition containing same | |
| EP1930358B1 (en) | Polyisocyanate composition and coating composition containing the same | |
| CN103820017B (en) | Epoxy modified polyurethane primer and preparation method thereof | |
| US8772434B2 (en) | Block polyisocyanate and urethane composition containing the same | |
| JP2007112936A (en) | Highly crosslinkable high solid urethane coating composition | |
| CN109486384A (en) | A kind of polyurea type Polyaspartic Ester-Based Coatings feedstock composition, from its coating and its preparation method and application | |
| CN109021801A (en) | A kind of aqueous silver dollar type metal flash paint of automobile and preparation method thereof | |
| JP2013224350A (en) | Polyisocyanate composition and paint composition containing the same | |
| CN110305547A (en) | A kind of water soluble acrylic acid amino-stoving varnish of low-temperature bake and preparation method thereof | |
| CN107815231A (en) | A kind of preparation method of waterborne anti-rust sealer | |
| CN108064256A (en) | Molding pearl reticulate pattern runway cover of one-component in-situ spraying and preparation method thereof | |
| CN113045971A (en) | Polyurea coating and preparation method thereof | |
| CN107828332B (en) | A kind of high solid two component polyurethane environmental protection coating material and preparation method thereof | |
| CN101643617A (en) | Water-based paint with metallic luster for vehicle and preparation method thereof | |
| CN109096897B (en) | Time-delay type aliphatic polyurethane finish paint | |
| CN110330880A (en) | A kind of anticorrosive paint, preparation method and application method | |
| JP5775660B2 (en) | High elongation, low temperature curable block polyisocyanate composition | |
| EP3584266B1 (en) | Polycarbodiimide composition, method for producing polycarbodiimide composition, water-dispersed composition, solution composition, resin composition, and resin cured article | |
| CN108610922B (en) | Coating composition, preparation method thereof, coating and method for protecting permanent magnet material | |
| CN100436560C (en) | Ultraviolet light curing coating and production thereof | |
| CN110452362B (en) | Water-based blocked isocyanate curing agent, preparation method thereof and water-based paint | |
| CN109535385A (en) | The preparation method of base polyurethane prepolymer for use as, preparation method and environmentally friendly polyureas sports ground surface layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190412 |
|
| RJ01 | Rejection of invention patent application after publication |