CN110452362A - Watersoluble closed isocyanate curing agent and preparation method thereof, water paint - Google Patents
Watersoluble closed isocyanate curing agent and preparation method thereof, water paint Download PDFInfo
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- CN110452362A CN110452362A CN201910767583.3A CN201910767583A CN110452362A CN 110452362 A CN110452362 A CN 110452362A CN 201910767583 A CN201910767583 A CN 201910767583A CN 110452362 A CN110452362 A CN 110452362A
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
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- 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
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08G18/80—Masked polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of watersoluble closed isocyanate curing agents and preparation method thereof, water paint.The watersoluble closed isocyanate curing agent, including following raw material: polyisocyanate trimer, poly glycol monomethyl ether, polyether Glycols, sealer, cosolvent, alkali metal alcoholates and neutralizer；Wherein, the polyisocyanates is selected from least one of aliphatic polyisocyante tripolymer and aromatic polyisocyanate tripolymer, the poly glycol monomethyl ether is selected from one of the polyglycol ether monohydric alcohol that molecular weight is 300~2000, and the molecular weight of the polyether Glycols is 120~1000.The watersoluble closed isocyanate curing agent can react with the resin of the active group such as amino resins, polyester resin in formulation for coating material, a large amount of soft segment structures are introduced in film, energy release when film can be delayed to be hit by stone, and then the anti-stoning energy of film is promoted, make film that there is resistance to hitting property of stone under the conditions of low film thickness.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of watersoluble closed isocyanate curing agent and its preparation side
Method, water paint.
Background technique
With advances in technology with the high speed of communications and transportation, automobile is more more and more universal, and car speed also greatly improves, this
While bringing great convenience, also to the surface covering of automobile, more stringent requirements are proposed.Automobile is as important family
The outer vehicles, in actual driving process, the surface covering of vehicle body, which may be subjected to, slides the weights such as material, road gallet
Shock, so that coating be made to peel off.Therefore, it is necessary to promote resistance to the hitting property of stone of automotive coatings, to reduce the weight such as road gallet
Object hits the injury to automotive coatings, to protect automobile.
Currently, traditional automotive coatings coating based on solvent type, generally designs coating thickness at 40 μm or so, it is reachable
The purpose hit to anti-stone.However, VOCs (volatile organic matter) discharge in solvent based coating is all harmful to human body and environment, with
The enhancing of environmental consciousness and the foundation of environmental regulation, traditional solvent type coating since VOCs content is exceeded, apply film thickness, by
Gradually it is eliminated.In recent years, new coating system is to surround how to reduce VOCs to design, however the thickness of film there are no mostly
It is obviously improved.For example, aqueous polyurethane floating coating has reached although which solve automobile-used floating coatings based on solvent type with water
For solvent, hence it is evident that reduce the pollution to environment, but aqueous polyurethane floating coating will reach corresponding required anti-stoning
Can, then coating thickness must be increased, usual coating thickness needs to reach 80 μm or more, and which greatly increases production costs.
In conclusion considering from the various aspects factor such as environmental protection, energy consumption, cost, major auto vendor is intended to meeting painting
Under the premise of film various aspects of performance, the thickness of reduction film as far as possible realizes the mesh of energy-saving and emission-reduction to reduce energy consumption, reduce cost
, to car paint film, more stringent requirements are proposed for this.Therefore, it needs to develop one kind under the conditions of low film thickness with preferably anti-stone
The auxiliary crosslinking and curing agent of performance is hit, anti-stoning energy of car paint film under the conditions of low film thickness is promoted with this.
Summary of the invention
Based on this, it is necessary to provide a kind of watersoluble closed isocyanate curing agent, the anti-stone for being able to ascend car paint film is hit
Performance.
A kind of watersoluble closed isocyanate curing agent, raw material include: polyisocyanate trimer, polyethyleneglycol first
Ether, polyether Glycols, sealer, cosolvent, alkali metal alcoholates and neutralizer；
Wherein, the polyisocyanate trimer is selected from aliphatic polyisocyante tripolymer and aromatic polyisocyanate
At least one of tripolymer, the poly glycol monomethyl ether are selected from the polyglycol ether monohydric alcohol that molecular weight is 300~2000
One of, the molecular weight of the polyether Glycols is 120~1000.
Above-mentioned watersoluble closed isocyanate curing agent, due to poly glycol monomethyl ether, polyether Glycols and polyisocyanates
Hydrophilic modifying and chain extending reaction occur for tripolymer, form it into backbone, and have hydrophily, the p- NCO group of sealer into
Row sealing end, keeps isocyanate group not active at normal temperature, realizes the closing of isocyanate group, and then obtain watersoluble closed isocyanide
Acid esters curing agent, while poly glycol monomethyl ether and polyether Glycols by selecting particular range molecular weight carry out hydrophilic modifying
And chain extension, make that its water dispersible is good, stability is good.
Above-mentioned watersoluble closed isocyanate curing agent improves the original of film anti-stoning energy in order to better understand the present invention
Reason delays energy so that existing largely to have in watersoluble closed isocyanate curing agent since polyether Glycols participate in chain extending reaction
The elastic construction of release is measured, shown in the structure of the moiety segments of the elastic construction such as following formula (I):
In formula (I), X is the main chain section of polyisocyanate trimer, and Y is the hydrogen for the terminal hydroxy group that poly glycol monomethyl ether is sloughed
Functional group afterwards, Z slough the functional group after the hydrogen of terminal hydroxy group for polyether Glycols, and B is after sealer sloughs reactive hydrogen atom
Functional group.
It should be noted that above-mentioned formula (I) is a kind of structural representation of the watersoluble closed isocyanate curing agent of the present invention,
Its absolute configuration is not represented.
The elastic construction can occur anti-with the resin of the active group such as amino resins, polyester resin in formulation for coating material
It answers, introduces a large amount of soft segment structures when forming film, energy release when film can be delayed to be hit by stone, and then promoted and applied
The anti-stoning energy of film makes film have resistance to hitting property of stone under the conditions of low film thickness.
In one of the embodiments, by weight percentage, raw material includes 25%~55% polyisocyanates trimerization
Body, 2%~15% poly glycol monomethyl ether, 0.1%~10% polyether Glycols, 15%~40% sealer, 2.8%~
30% cosolvent, 0.05%~0.5% alkali metal alcoholates and 0.05%~0.5% neutralizer.
The polyether Glycols are in diethylene glycol, polyethylene glycol and polypropylene glycol in one of the embodiments,
It is at least one；And/or
The sealer is selected from malonic ester blocked dose, at least one of amino sealer and oxime sealer；And/or
The cosolvent is selected from least one of the saturation unitary fatty alkyl alcohol with 1~8 carbon atom；And/or
The alkali metal alcoholates are in potassium tert-butoxide, sodium methoxide, methanol solution of sodium methylate and alcohol sodium alcohol solution
It is at least one；And/or
The neutralizer is selected from least one of phosphoric acid and sulfuric acid.
The polyether Glycols are polyethylene glycol or polypropylene glycol in one of the embodiments,；And/or
The sealer is malonic ester blocked dose；And/or
The polyisocyanate trimer is selected from isophorone diisocyanate (IPDI) tripolymer, two isocyanide of hexa-methylene
At least one of acid esters (HDI) tripolymer and toluene di-isocyanate(TDI) (TDI) tripolymer.
The molecular weight of the poly glycol monomethyl ether is 300~1000 in one of the embodiments, the polyethers binary
The molecular weight of alcohol is 120~1000, and the sealer is malonic ester blocked dose, and malonic ester blocked dose of the ester group is tool
There is the alkoxyl formyl of 1~8 carbon atom.
Another object of the present invention is to provide a kind of preparation method of watersoluble closed isocyanate curing agent, including following step
It is rapid:
Poly glycol monomethyl ether, polyether Glycols and polyisocyanates are subjected to hydrophilic modifying and chain extension, obtain amino first
Acid esters prepolymer；Wherein, the poly glycol monomethyl ether is in the polyglycol ether monohydric alcohol that molecular weight is 300~2000
One kind, the molecular weight of the polyether Glycols are 120~1000, and the polyisocyanate trimer is selected from aliphatic polyisocyanic acid
At least one of ester tripolymer and aromatic polyisocyanate tripolymer；
Sealer and alkali metal alcoholates progress is pre-dispersed, obtain dispersion；
The carbamate prepolymer is blocked under the conditions of 60 DEG C~80 DEG C with the dispersion, obtains mixture,
And control in the mixture-residual volume of NCO group is less than or equal to 0.4wt%；
The mixture and neutralizer are mixed and adjust pH value, then removes solvent, cosolvent is added and adjusts solid content, mistake
Filter, obtains the watersoluble closed isocyanate curing agent.
The temperature of the hydrophilic modifying and chain extension is 40 DEG C~90 DEG C in one of the embodiments,；The removal solvent
Condition are as follows: vacuum degree be -0.1MPa~-0.099MPa, temperature be 60 DEG C~80 DEG C.
It is 7~10 that pH value is adjusted after in one of the embodiments, mixing the mixture and neutralizer, and hydrotropy is added
It is 70wt%~90wt% that agent, which adjusts solid content,.
Yet another object of that present invention is to a kind of water paint is provided, which includes that above-mentioned watersoluble closed isocyanates is solid
Agent uses watersoluble closed isocyanate curing agent made from above-mentioned preparation method.
The water paint further includes matrix resin in one of the embodiments, and the matrix resin is selected from amino tree
At least one of rouge and polyester resin.
Compared with prior art, the invention has the following advantages:
(1) watersoluble closed isocyanate curing agent water dispersible of the invention is good, stability is good, and has and energy is delayed to release
The elastic construction of effect is put, a large amount of soft segment structures can be introduced in the film of formation with the resin reaction in formulation for coating material,
To help film to carry out energy release when being hit by stone, coating anti-stoning energy of film under the conditions of low film thickness is promoted.
(2) solid content of watersoluble closed isocyanate curing agent of the invention is high, no volatile NCO, no aromatic hydrocarbons, ether
Class solvent, low VOCs discharge.
(3) the watersoluble closed isocyanate curing agent of the present invention to prepare synthesis technology simple, it is easy to accomplish.
(4) anti-stoning of water paint of the present invention can be good, enables film when reaching corresponding anti-stoning and requiring, film
Thickness decline reduces VOCs discharge, can reduce energy consumption and cost.
Detailed description of the invention
Fig. 1 is the infared spectrum of the watersoluble closed isocyanate curing agent of the embodiment of the present invention 1；
Fig. 2 is the infared spectrum of the watersoluble closed isocyanate curing agent of the embodiment of the present invention 2；
Fig. 3 is the infared spectrum of the watersoluble closed isocyanate curing agent of the embodiment of the present invention 3；
Fig. 4 is the infared spectrum of the watersoluble closed isocyanate curing agent of the embodiment of the present invention 4；
Fig. 5 is the infared spectrum of the watersoluble closed isocyanate curing agent of the embodiment of the present invention 5.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
An embodiment of the present invention provides a kind of watersoluble closed isocyanate curing agent, and raw material includes: polyisocyanates
Tripolymer, poly glycol monomethyl ether, polyether Glycols, sealer, cosolvent, alkali metal alcoholates and neutralizer；
Wherein, polyisocyanate trimer is selected from aliphatic polyisocyante tripolymer and aromatic polyisocyanate trimerization
At least one of body, poly glycol monomethyl ether are selected from one of the polyglycol ether monohydric alcohol that molecular weight is 300~2000,
The molecular weight of polyether Glycols is 120~1000.
Aliphatic polyisocyante tripolymer is selected from the aliphatic polyisocyante tripolymer and hydrocarbon that alkyl is linear chain structure
One of alicyclic polyisocyanates tripolymer in base containing carbocyclic ring.
In this way, carrying out hydrophilic modifying and chain extension to polyisocyanates by poly glycol monomethyl ether and polyether Glycols, obtain
To the watersoluble closed isocyanate curing agent of the elastic construction with long chain, not only water dispersible is good, and stability is good.
Researcher has found under study for action, when poly glycol monomethyl ether, polyether Glycols molecular weight are smaller, usually moisture
Dissipate after cannot be stable dispersion；And molecular weight it is larger when, the crystallinity of obtained watersoluble closed isocyanate curing agent compared with
By force, water dispersible is poor.Therefore, select molecular weight for 300~2000 polyglycol ether monohydric alcohol, molecular weight be 100~
1000 polyether Glycols carry out hydrophilic modifying and chain extension to polyisocyanate trimer, and obtained watersoluble closed isocyanates is solid
Agent water dispersible is good, and stability is good.
In one embodiment, by weight percentage, raw material include 25%~55% polyisocyanate trimer,
2%~15% poly glycol monomethyl ether, 0.1%~10% polyether Glycols, 15%~40% sealer, 2.8%~30% help
Solvent, 0.05%~0.5% alkali metal alcoholates and 0.05%~0.5% neutralizer.
Further, by weight percentage, raw material include 30%~55% polyisocyanate trimer, 4%~
12% poly glycol monomethyl ether, 0.5%~10% polyether Glycols, 15%~40% sealer, 5%~30% cosolvent,
0.05%~0.5% alkali metal alcoholates and 0.05%~0.5% neutralizer.
In one embodiment, polyisocyanate trimer is selected from isophorone diisocyanate trimer, hexa-methylene two
At least one of isocyanate trimer and toluene diisocyanate trimer.
More preferably, polyisocyanate trimer is selected from isophorone diisocyanate trimer and hexa-methylene diisocyanate
At least one of ester tripolymer.
In one embodiment, the molecular weight of poly glycol monomethyl ether is 300~1000.
In one embodiment, the molecular weight of polyether Glycols is 120~1000.
In one embodiment, polyether Glycols are selected from least one of diethylene glycol, polyethylene glycol and polypropylene glycol.
More preferably, polyether Glycols be selected from molecular weight be 120~1000 polyethylene glycol and molecular weight be 120~1000
At least one of polypropylene glycol.
In one embodiment, sealer in malonic ester blocked dose, amino sealer and oxime sealer at least one
Kind.
In one embodiment, sealer is malonic ester blocked dose, and malonic ester blocked dose of the ester group is C1~C8
Alkoxyl formyl, i.e., malonic ester blocked dose of ester group is the alkoxyl formyl containing 1~8 carbon atom.
For example, sealer can be selected from the ester groups such as dimethyl malenate, Diisopropyl malonate and malonic acid di-n-octyl is
At least one of the compound of alkoxyl formyl with 1~8 carbon atom.
In one embodiment, cosolvent is selected from least one be saturated in unitary fatty alkyl alcohol with 1~8 carbon atom
Kind.Such as methanol, isopropanol, n-octyl alcohol etc..
In one embodiment, alkali metal alcoholates are selected from potassium tert-butoxide, sodium methoxide, methanol solution of sodium methylate and sodium ethoxide ethyl alcohol
At least one of solution.
In one embodiment, neutralizer is selected from least one of phosphoric acid and sulfuric acid.
Another embodiment of the present invention is to provide a kind of preparation method of above-mentioned watersoluble closed isocyanate curing agent, packet
Include following steps S1~S4.
S1, poly glycol monomethyl ether, polyether Glycols and polyisocyanates are subjected to hydrophilic modifying and chain extension, obtain amino
Urethane prepolymer.
In one embodiment, carry out hydrophilic modifying and the step of chain extension before, further include to poly glycol monomethyl ether and
The step of polyether Glycols are dehydrated, the water content for controlling the poly glycol monomethyl ether and the polyether Glycols are less than
0.1wt%.
Further, the condition of the dehydration includes: that vacuum degree is less than or equal to -0.099MPa, and temperature is 80 DEG C~105
DEG C, the time is 0.5h~4h.
More preferably, vacuum degree is -0.1MPa~-0.099MPa.
In one embodiment, the temperature of hydrophilic modifying and chain extension is 40 DEG C~90 DEG C.
Specifically, poly glycol monomethyl ether, polyethylene glycol and toluene are mixed, then decompression dehydration, utilizes toluene and water
Azeotropic vaporization takes away the water in poly glycol monomethyl ether and polyethylene glycol, makes the mixture of poly glycol monomethyl ether and polyethylene glycol
Water content is in 0.01wt%~0.1wt%；The mixture is uniformly mixed with polyisocyanates, organic solvent again, is warming up to 40
DEG C~90 DEG C, 1h~3h is reacted, carbamic acid acid prepolymer is obtained.
Further, the dosage of toluene is the 5%~15% of poly glycol monomethyl ether and polyethylene glycol weight；Organic solvent
Dosage be polyisocyanates weight 10%~20%, organic solvent can be selected from ethyl acetate, acetone and butanone etc..
S2, sealer and alkali metal alcoholates are carried out pre-dispersed, obtains dispersion.
Specifically, sealer and alkali metal alcoholates is pre-dispersed at room temperature.
In this way, it is first that sealer and alkali metal alcoholates progress is pre-dispersed, so that sealer and alkali metal alcoholates is uniformly dispersed, grasps
Facilitate, and can effectively improve catalytic efficiency.
It it should be understood that the sequence of step S1 and S2 are in no particular order, can carry out simultaneously, one can also be selected and first complete to walk
Rapid S1 or step S2.
S3, the dispersion for obtaining carbamate prepolymer and step S2 that step S1 is obtained are in 60 DEG C~80 DEG C conditions
Lower sealing end, obtains mixture, and control in the mixture-residual volume of NCO group is less than or equal to 0.4wt%.
In one embodiment, the sealing end time is 3h~8h.
S4, the mixture of step S3 and neutralizer are mixed into adjusting pH value, then removes solvent, cosolvent is added and adjusts admittedly
Content, filtering, obtains watersoluble closed isocyanate curing agent.
Specifically, neutralizer is added into the mixture of step S3, adjusts the pH value of mixture, then decompression removal solvent
Afterwards, cosolvent is added, adjusts the solid content of mixed system, obtains watersoluble closed isocyanate curing agent.
In one embodiment, remove the condition of solvent are as follows: vacuum degree be -0.1MPa~-0.099MPa, temperature be 60 DEG C~
80℃。
In one embodiment, the pH value of watersoluble closed isocyanate curing agent is 7~10, watersoluble closed cured with isocyanates
The solid content of agent is 70wt%~90wt%.
Yet another object of that present invention is to a kind of water paint is provided, which includes that above-mentioned watersoluble closed isocyanates is solid
Agent uses watersoluble closed isocyanate curing agent made from above-mentioned preparation method.
Water paint further includes matrix resin in one of the embodiments, and matrix resin is selected from amino resins and polyester
At least one of resin.
The present invention contains the water paint of above-mentioned watersoluble closed isocyanate curing agent, since watersoluble closed isocyanates is solid
Agent has elastic construction, can react with the matrix resin in water paint, to introduce a large amount of flexible chains in film
Segment structure makes film release energy when being hit by stone, promotes anti-stoning energy of film under the conditions of low film thickness.
The following are specific embodiments
NCO residual volume is surveyed referring to " polymethylene multi-phenenyl isocyanate radical content measuring method " in GB12009.4-89
；
Anti- stone hits grade and according to DIN EN ISO 20567-1 carries out resistance to stone and hit test method measuring；
Impact grade carries out impact test methods according to GB1732-79 and measures；
The convex grade of cup carries out the convex test method of cup according to GB/T 9753-2007 and measures；
In case of no particular description, raw materials used to be all made of commercial product.
It is each embodiment charge ratio below, as shown in table 1.
Table 1
Note: "-" expression is not added, similarly hereinafter.
Each embodiment the preparation method is as follows:
Embodiment 1
(1) poly glycol monomethyl ether (MPEG1000) and polyethylene glycol (PEG1000) are placed in four round flask, are added
Enter toluene (dosage of toluene is the 10% of poly glycol monomethyl ether weight), is inserted into thermometer, later on oil pump, decompression water removal is (very
Reciprocal of duty cycle is -0.099MPa, and temperature is 80 DEG C, time 4h), the water content of terminal point control mixture is 0.07%, is cooled to 40 DEG C.
(2) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in above-mentioned four round flask, in stirring
Under, ethyl acetate (dosage of ethyl acetate is the 10%~20% of reaction system total volume), HDI trimer polyisocyanate cyanogen is added
Acid esters, while it being blown into nitrogen, disperse 15min, then heat to 90 DEG C, stopping is blown into nitrogen, reacts 2h, obtains carbamate
Prepolymer.
(3) by the alkaline metal salt of alcohol (sodium methoxide) with malonic ester blocked dose (Diisopropyl malonate) at room temperature
It is pre-dispersed, obtain malonate and alkali metal alcoholates dispersion.
(4) completely after completion of the reaction to carbamate prepolymer, it cools to 30 DEG C, by step (3) dispersion
Body carries out sealing end 8h under the conditions of 60 DEG C, and until measuring NCO≤0.4%, sealing end terminates, and stops reaction.
(5) phosphoric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Isopropanol is added,
Adjusting amount of solid content is 75.16%, and adjustment pH value is 8.0, adds 400 mesh diatomite filtering and dischargings, and the promotion can be made
The watersoluble closed isocyanate curing agent of film anti-stoning energy.
Embodiment 2
(1) poly glycol monomethyl ether (mpeg 3 00) and polyethylene glycol (PEG500) are placed in four round flask, are added
The toluene 10wt% of poly glycol monomethyl ether (dosage be), is inserted into thermometer, later on oil pump, decompression water removal (vacuum degree is-
0.099MPa, temperature are 99 DEG C, time 2h), the water content of terminal point control mixture is 0.1%, is cooled to 40 DEG C.
(2) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed 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 90 DEG C,
Stopping is blown into nitrogen, reacts 2h, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (potassium tert-butoxide) with malonic ester blocked dose (dimethyl malenate) at room temperature
It is pre-dispersed, obtain malonate and alkali metal alcoholates dispersion.
(4) completely after completion of the reaction to carbamate prepolymer, it cools to 30 DEG C, by step (3) dispersion
Body carries out sealing end 5h under the conditions of 70 DEG C, and until measuring NCO≤0.4%, sealing end terminates, and stops reaction.
(5) sulfuric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Methanol is added, adjusts
Whole amount of solid content is 80%, and adjustment pH value is 7.5, adds 400 mesh diatomite filtering and dischargings, and the promotion film that can be made described is anti-
Stone hits the watersoluble closed isocyanate curing agent of performance.
Embodiment 3
(1) poly glycol monomethyl ether (MPEG600) and polypropylene glycol (PPG500) are placed in four round flask, are added
The toluene 10wt% of poly glycol monomethyl ether (dosage be), is inserted into thermometer, later on oil pump, decompression water removal (vacuum degree is-
0.099MPa, temperature are 105 DEG C, time 0.5h), the water content of terminal point control mixture is 0.07%, is cooled to 40 DEG C.
(2) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed 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 90 DEG C, stop
It is only blown into nitrogen, 2h is reacted, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (methanol solution of sodium methylate) and malonic ester blocked dose of (malonic acid di-n-octyl) In
It is pre-dispersed at room temperature, obtain malonate and alkali metal alcoholates dispersion.
(4) completely after completion of the reaction to carbamate prepolymer, it cools to 30 DEG C, by step (3) dispersion
Body carries out sealing end 3h under the conditions of 80 DEG C, and until measuring NCO≤0.4%, sealing end terminates, and stops reaction.
(5) phosphoric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；N-octyl alcohol is added,
Adjusting amount of solid content is 90%, and adjustment pH value is 9.0, adds 400 mesh diatomite filtering and dischargings, and the promotion film can be made
The watersoluble closed isocyanate curing agent of anti-stoning energy.
Embodiment 4
(1) poly glycol monomethyl ether (MPEG600) and polyethylene glycol (PEG1000) are placed in four round flask, are added
Enter toluene (poly glycol monomethyl ether 10wt%), be inserted into thermometer, later on oil pump, decompression water removal (vacuum degree be-
0.099MPa, temperature are 99 DEG C, time 4h), the water content of terminal point control mixture is 0.07%, is cooled to 40 DEG C.
(2) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed 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 90 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 malonic ester blocked dose of (Diisopropyl malonate) In
It is pre-dispersed at room temperature, obtain malonate and alkali metal salt dispersion.
(4) completely after completion of the reaction to carbamate prepolymer, it cools to 30 DEG C, by step (3) dispersion
Body carries out sealing end 5h under the conditions of 70 DEG C, and until measuring NCO≤0.4%, sealing end terminates, and stops reaction.
(5) phosphoric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Isopropanol is added,
Adjusting amount of solid content is 70%, and adjustment pH value is 8.0, adds 400 mesh diatomite filtering and dischargings, and the promotion film can be made
The watersoluble closed isocyanate curing agent of anti-stoning energy.
Embodiment 5
(1) poly glycol monomethyl ether (MPEG600) and diethylene glycol are placed in four round flask, it is (poly- that toluene is added
Glycol monoethyl ether 10wt%), it is inserted into thermometer, later on oil pump, (vacuum degree is -0.099MPa, and temperature is for decompression water removal
80 DEG C, time 4h), the water content of terminal point control mixture is 0.07%, is cooled to 40 DEG C.
(2) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed 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 90 DEG C, stop
It is only blown into nitrogen, 2h is reacted, obtains carbamate prepolymer.
(3) by the alkaline metal salt of alcohol (sodium methoxide) with malonic ester blocked dose (Diisopropyl malonate) at room temperature
It is pre-dispersed, obtain malonate and alkali metal salt dispersion.
(4) completely after completion of the reaction to carbamate prepolymer, it cools to 30 DEG C, by step (3) dispersion
Body carries out sealing end 5h under the conditions of 70 DEG C, and until measuring NCO≤0.4%, sealing end terminates, and stops reaction.
(5) phosphoric acid is added, neutralizes 20min, decompression abstraction solvent, measuring amount of solid content is 100%；Isopropanol is added,
Adjusting amount of solid content is 75%, and adjustment pH value is 8.0, adds 400 mesh diatomite filtering and dischargings, and the promotion film can be made
The watersoluble closed isocyanate curing agent of anti-stoning energy.
Performance test
1 and the watersoluble closed isocyanate curing agent of Examples 1 to 5 is scanned respectively using infrared spectrometer, institute
The infared spectrum obtained is as shown in Fig. 1~5.
2, according to formulation for coating material as shown in Table 2, by the aqueous of promotion film anti-stoning energy made from Examples 1 to 5
Blocked isocyanate curing agent is configured to corresponding water paint 1~5 and comparison coating 1, Cohan woundBL
Coating in contrast with 2867 watersoluble closed polyisocyanate curing agents preparations, carries out the relevant evaluation of coating performance parameter.
Wherein, coating 1 " being prepared according to the curing agent in coating 1 is compared in table 2 " is compared
Table 2
Water paint 1~5 and comparison coating 1~2 are made to the floating coat of different-thickness, use 508 Erichsen multiples impacts
Instrument, carries out anti-stone according to DIN EN ISO 20567-1 standard and hits experiment test, and it is real to carry out impact according to GB1732-79 standard
Test examination carries out the convex experiment test of cup according to GB/T 9753-2007 standard, and experimental result is as shown in table 3.
Table 3
It is tested from 3 coating performance parameter of table it is found that being created with CohanThe watersoluble closed polyisocyanic acid of BL 2867
Ester curing agent is compared, and the Examples 1 to 5 watersoluble closed isocyanate curing agent obtained for promoting film anti-stoning energy is in low film
Under the conditions of thickness, anti-stone hits grade, impact grade, and the convex grade of cup is substantially better thanBL 2867, in high film thickness condition
Under also have obvious advantage, can be obviously improved film anti-stoning energy, impact grade, the convex grade of cup；It also examines simultaneously
The indices such as appearance of film, acidproof, alkaline-resisting, weather-proof have been surveyed, performance requirement is able to satisfy.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of watersoluble closed isocyanate curing agent, which is characterized in that its raw material includes: polyisocyanate trimer, poly- second
Glycol monomethyl ether, polyether Glycols, sealer, cosolvent, alkali metal alcoholates and neutralizer；
Wherein, the polyisocyanate trimer is selected from aliphatic polyisocyante tripolymer and aromatic polyisocyanate trimerization
At least one of body, the poly glycol monomethyl ether is in the polyglycol ether monohydric alcohol that molecular weight is 300~2000
One kind, the molecular weight of the polyether Glycols are 120~1000.
2. watersoluble closed isocyanate curing agent according to claim 1, which is characterized in that by weight percentage,
Raw material includes 25%~55% polyisocyanate trimer, 2%~15% poly glycol monomethyl ether, 0.1%~10% polyethers two
First alcohol, 15%~40% sealer, 2.8%~30% cosolvent, 0.05%~0.5% alkali metal alcoholates and 0.05%~
0.5% neutralizer.
3. watersoluble closed isocyanate curing agent according to claim 1 or 2, which is characterized in that the polyether Glycols
Selected from least one of diethylene glycol, polyethylene glycol and polypropylene glycol；And/or
The sealer is selected from malonic ester blocked dose, at least one of amino sealer and oxime sealer；And/or
The cosolvent is selected from least one of the saturation unitary fatty alkyl alcohol with 1~8 carbon atom；And/or
The alkali metal alcoholates in potassium tert-butoxide, sodium methoxide, methanol solution of sodium methylate and alcohol sodium alcohol solution at least
It is a kind of；And/or
The neutralizer is selected from least one of phosphoric acid and sulfuric acid.
4. watersoluble closed isocyanate curing agent according to claim 3, which is characterized in that the polyether Glycols are poly-
One of ethylene glycol and polypropylene glycol；And/or
The sealer is malonic ester blocked dose；And/or
The polyisocyanate trimer is selected from isophorone diisocyanate trimer, hexamethylene diisocyanate trimer
At least one of with toluene diisocyanate trimer.
5. watersoluble closed isocyanate curing agent according to any one of claims 1 to 4, which is characterized in that the poly- second
The molecular weight of glycol monomethyl ether is 300~1000, and the molecular weight of the polyether Glycols is 120~1000, and the sealer is
Malonic ester blocked dose, malonic ester blocked dose of the ester group is the alkoxyl formyl with 1~8 carbon atom.
6. a kind of preparation method of watersoluble closed isocyanate curing agent, which comprises the following steps:
Poly glycol monomethyl ether, polyether Glycols and polyisocyanates are subjected to hydrophilic modifying and chain extension, obtain carbamate
Prepolymer；Wherein, the poly glycol monomethyl ether is one in 300~2000 polyglycol ether monohydric alcohol selected from molecular weight
Kind, the molecular weight of the polyether Glycols is 120~1000, and the polyisocyanate trimer is selected from aliphatic polyisocyante
At least one of tripolymer and aromatic polyisocyanate tripolymer；
Sealer and alkali metal alcoholates progress is pre-dispersed, obtain dispersion；
The carbamate prepolymer is blocked under the conditions of 60 DEG C~80 DEG C with the dispersion, obtains mixture, and control
Make in the mixture-residual volume of NCO group is less than or equal to 0.4wt%；
The mixture and neutralizer are mixed, solvent is then removed, cosolvent is added, filtering obtains described watersoluble closed different
Cyanate curing agent.
7. preparation method according to claim 6, which is characterized in that the temperature of the hydrophilic modifying and chain extension be 40 DEG C~
90℃；The condition of the removal solvent are as follows: vacuum degree is -0.1MPa~-0.099MPa, and temperature is 60 DEG C~80 DEG C.
8. preparation method according to claim 6 or 7, which is characterized in that adjusted after mixing the mixture and neutralizer
Saving pH value is 7~10, and it is 70wt%~90wt% that cosolvent, which is added, and adjusts solid content.
9. a kind of water paint, which is characterized in that the water paint includes the described in any item aqueous envelopes of Claims 1 to 5
Close isocyanate curing agent or solid using watersoluble closed isocyanates made from any one of claim 6~8 preparation method
Agent.
10. water paint according to claim 9, which is characterized in that the water paint further includes matrix resin, described
Matrix resin is selected from least one of amino resins and polyester resin.
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