CN110483738A - Blocked isocyanate curing agent and preparation method thereof, one-component coating - Google Patents
Blocked isocyanate curing agent and preparation method thereof, one-component coating Download PDFInfo
- Publication number
- CN110483738A CN110483738A CN201910767592.2A CN201910767592A CN110483738A CN 110483738 A CN110483738 A CN 110483738A CN 201910767592 A CN201910767592 A CN 201910767592A CN 110483738 A CN110483738 A CN 110483738A
- Authority
- CN
- China
- Prior art keywords
- isocyanate curing
- blocked isocyanate
- curing agent
- trimer
- sealer
- 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
- C08G18/28—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
- C08G18/302—Water
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- 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
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8038—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3225
Abstract
The present invention relates to a kind of blocked isocyanate curing agents and preparation method thereof, one-component coating.The raw material of the blocked isocyanate curing agent includes: polyisocyanate trimer, chain extender, sealer and cosolvent；Wherein, the polyisocyanate trimer is selected from least one of isophorone diisocyanate trimer, hexamethylene diisocyanate trimer and toluene diisocyanate trimer, the chain extender is selected from least one of the polyfunctional compound containing hydroxyl and/or amino and water, and the polyfunctional compound has 2~12 carbon atoms.The blocked isocyanate curing agent has the cross-linked structure of more crosslink sites, and with amino resins, the acrylic resin etc. in varnish paint formula the crosslinking of multidigit point can occur for blocked isocyanate curing agent tripolymer, so as to promote the crosslink density of film.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of blocked isocyanate curing agent and preparation method thereof,
One-component coating.
Background technique
Blocked isocyanate curing agent be a kind of room temperature do not solidify, the cured resin of the auxiliary of stable storing, due to its tool
There is outstanding stability, therefore is widely used in the 1K of car paint (one pack system) varnish paint.
However the paint film crosslink density that blocked isocyanate curing agent currently on the market obtains when varnish curing is inadequate
Height influences water resistance, the chemical-resistance of paint film.For example, a kind of with pyrazole derivative compounds and active methylene compound
Compound closure agent is to polyisocyanates progress NCO sealing end, obtained blocked polyisocyanates, although storage stability is preferable,
It is limited to the crosslink density for improving film.Another kind malonate and the mixture of triazole block polyisocyanates
Blocked polyisocyanate, can be used as the crosslinking agent of polyurethane baking vanish, prevent from crystallizing and improving enclosed type polyisocyanate in a solvent
The performance of the heated yellowing of cyanate, it is still, also very limited to the crosslink density for improving film.
Therefore, from curing agent angle, a kind of new blocked isocyanate curing agent is developed, 1K varnish film is promoted
Crosslink density, become particularly important.
Summary of the invention
Based on this, it is necessary to provide a kind of blocked isocyanate curing agent with high crosslink density, can effectively be promoted
The crosslink density of automobile varnish film.
A kind of blocked isocyanate curing agent, raw material include: polyisocyanate trimer, chain extender, sealer and help
Solvent；
Wherein, the polyisocyanate trimer is selected from isophorone diisocyanate trimer, two isocyanide of hexa-methylene
At least one of acid esters tripolymer and toluene diisocyanate trimer, the chain extender, which is selected from, contains hydroxyl and/or amino
Polyfunctional compound and at least one of water, the polyfunctional compound has 2~12 carbon atoms.
Above-mentioned blocked isocyanate curing agent, with the polyfunctional compound containing hydroxyl and/or amino or water and polyisocyanate
Cyanate tripolymer carries out chain extending reaction, forms it into backbone, and with sealer in polyisocyanate trimer-
NCO group is blocked, and is kept isocyanate group not active at normal temperature, is realized the closing of isocyanate group, obtains closing different
Cyanate curing agent, the closing isocyanide ester curing agent solution are honored as a queen with multiple crosslink sites, and multiple crosslink sites can be with painting
Active group in the resin components such as polyester resin, acrylic resin, amino resins in material crosslinks reaction, to use
The blocked isocyanate curing agent can be improved the crosslink density of 1K varnish film.
Above-mentioned blocked isocyanate curing agent has the structural unit as shown in following formula (I) or formula (II):
It should be noted that formula (I) is the preparation using the polyfunctional compound containing hydroxyl and/or amino as chain extender
The segmented structure unit of obtained blocked isocyanate curing agent, formula (II) are the closing isocyanides being prepared using water as chain extender
The segmented structure unit of acid esters curing agent.Wherein, X is the main chain section of polyisocyanate trimer, and R is to contain 2~12 carbon originals
The saturated alkyl of son, Y and Z are separately selected from one of N and O, and B is that sealer sloughs the function after reactive hydrogen atom
Group.
Above-mentioned blocked isocyanate curing agent can be with amino resins, polyester resin and the acrylic acid tree in varnish paint formula
The resin of the active group such as rouge reacts, since the Trimeric structures of the closing isocyanide acid as curing agent have multiple crosslinkings
Site structure, so as to promote the crosslink density after curing of coating.
In one of the embodiments, by weight percentage, raw material includes 50%~68% polyisocyanates trimerization
Body, 0.5%~10% chain extender, 5%~26% sealer and 10%~25% cosolvent.
The chain extender is selected from water, the glycol with 2~12 carbon atoms, diamines and alcohol in one of the embodiments,
At least one of amine；And/or
The sealer is selected from least one of amino sealer, oximido sealer and hydroxyl sealer.
The polyisocyanate trimer is selected from isophorone diisocyanate (IPDI) three in one of the embodiments,
At least one of aggressiveness and hexamethylene diisocyanate (HDI) tripolymer；And/or
The sealer in 3,5- dimethyl pyrazole, 1,2,4- triazole, isopropylamine and methyl ethyl ketoxime at least one
Kind；And/or
The cosolvent is the mixture of trimethylbenzene and propylene glycol methyl ether acetate.
The chain extender is selected from the saturated alkyl glycol with 2~12 carbon atoms, has in one of the embodiments,
In two hydro diamine of saturated alkyl of 2~12 carbon atoms, the saturated alkyl glycol amine with 2~12 carbon atoms and water at least
It is a kind of.
Another object of the present invention is to provide a kind of preparation method of blocked isocyanate curing agent, comprising the following steps:
Chain extender and polyisocyanate trimer are mixed, chain extension, obtains prepolymer；Wherein, the polyisocyanates three
Aggressiveness is selected from isophorone diisocyanate trimer, hexamethylene diisocyanate trimer and toluene di-isocyanate(TDI) trimerization
At least one of body, at least one in polyfunctional compound of the chain extender selected from water and containing hydroxyl and/or amino
Kind, the multifunctional dough object has 2~12 carbon atoms；
The prepolymer and sealer are blocked under the conditions of 60 DEG C~80 DEG C, obtain mixture；
The solid content that cosolvent adjusts the mixture is added, obtains the blocked isocyanate curing agent.
The method of the present invention with the polyfunctional compound containing hydroxyl and/or amino or water and polyisocyanate trimer into
Row chain extending reaction forms it into backbone, and is blocked with the p- NCO group of sealer, makes isocyanate group at normal temperature
It is not active, it realizes the closing of isocyanate group, obtains the blocked isocyanate curing agent with multiple crosslink sites, this method
Preparation process is simple, can obtain having high crosslinking after the resin solidification of the blocked isocyanate curing agent and hydroxyl that are prepared
The film of density has excellent water-fast chemical resistance.
In one of the embodiments, the step of sealing end control in the mixture-residual qualities of NCO group are small
In or equal to 0.1%.
In one of the embodiments, it is described be added cosolvent adjust the solid content of the mixture to 75wt%~
90wt%.
Yet another object of that present invention is to a kind of one-component coating is provided, which includes above-mentioned closing isocyanic acid
Ester curing agent uses blocked isocyanate curing agent made from above-mentioned preparation method.
The one-component coating further includes matrix resin in one of the embodiments, and the matrix resin is selected from amino
At least one of resin, polyester resin and acrylic resin.
Compared with prior art, the invention has the following advantages:
(1) blocked isocyanate curing agent of the invention has the cross-linked structure of more crosslink sites, in formulation for coating material
Resin reaction, the tripolymer that isocyanide acid as curing agent is closed in the film of formation can crosslink, so as to promote film
Crosslink density, improve water resistance and chemical resistance.
(2) solid content of blocked isocyanate curing agent of the invention is high, no volatile NCO, and there is lower VOC to contain
Amount.
(3) inventive closure isocyanate curing agent to prepare synthesis technology simple, it is easy to accomplish.
Detailed description of the invention
Fig. 1 is the infared spectrum of 1 blocked isocyanate curing agent of the embodiment of the present invention；
Fig. 2 is the infared spectrum of 4 blocked isocyanate curing agent of the embodiment of the present invention；
Fig. 3 is the infared spectrum of 7 blocked isocyanate curing agent of the embodiment of the present invention.
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 blocked isocyanate curing agent, and raw material includes: polyisocyanates trimerization
Body, chain extender, sealer and cosolvent；
Wherein, polyisocyanate trimer is selected from isophorone diisocyanate trimer, hexamethylene diisocyanate
At least one of tripolymer and toluene diisocyanate trimer, chain extender are selected from water and more containing hydroxyl and/or amino
At least one of functional compounds, the polyfunctional compound have 2~12 carbon atoms.
In one embodiment, by weight percentage, blocked isocyanate curing agent raw material includes more than 50%~68%
Isocyanate trimer, 0.5%~10% chain extender, 5%~26% sealer and 10%~25% cosolvent.
More preferably, polyisocyanate trimer is selected from isophorone diisocyanate trimer and hexa-methylene diisocyanate
At least one of ester tripolymer.
In one embodiment, chain extender in water, the glycol with 2~12 carbon atoms, diamines and hydramine at least
It is a kind of.
Further, chain extender is selected from saturated alkyl glycol with 2~12 carbon atoms, with 2~12 carbon atoms
At least one of two hydro diamine of saturated alkyl, the saturated alkyl glycol amine with 2~12 carbon atoms and water.
More preferably, chain extender be selected from ethylene glycol, 1,6- hexylene glycol, 1,12- dodecanediol, ethylenediamine, 1,6- oneself two
One of amine, 1,12- dodecyl diamines, ethanol amine and water.
In one embodiment, sealer is selected from least one of amino sealer, oximido sealer and hydroxyl sealer.
Further, sealer is in 3,5- dimethyl pyrazole, 1,2,4- triazoles, diisopropylamine and methyl ethyl ketoxime
It is at least one.
More preferably, sealer is selected from least one of 3,5- dimethyl pyrazole, diisopropylamine and methyl ethyl ketoxime.
In one embodiment, cosolvent is selected from least one of trimethylbenzene and propylene glycol methyl ether acetate (PMA).
More preferably, cosolvent is the mixture of trimethylbenzene and propylene glycol methyl ether acetate.
Further, the volume ratio of trimethylbenzene and propylene glycol methyl ether acetate is (1.8~2.2): 1.
In one embodiment, by weight percentage, the raw material of blocked isocyanate curing agent includes: more than 60%~65%
Isocyanate trimer, 2%~8% chain extender, 22%~28% sealer and 10%~15% cosolvent；Polyisocyanates three
Aggressiveness is HDI trimer, and chain extender is the glycol with 2~12 carbon atoms, and sealer is methyl ethyl ketoxime.
It is more advantageous to the crosslink density for improving film with the blocked isocyanate curing agent that above-mentioned raw materials are prepared, and makes
Standby operation is more convenient.
Another embodiment of the present invention is to provide a kind of preparation method of above-mentioned blocked isocyanate curing agent, including with
Lower step S1~S3.
S1, chain extender and polyisocyanate trimer are mixed, chain extension, obtains prepolymer.
Wherein, the polyisocyanate trimer is selected from isophorone diisocyanate trimer, two isocyanide of hexa-methylene
At least one of acid esters tripolymer and toluene diisocyanate trimer, the chain extender, which is selected from, contains hydroxyl and/or amino
Polyfunctional compound and at least one of water, the multifunctional dough object has the alkyl of 2~12 carbon atoms.
In one embodiment, with water or be the diol chain-extension agent with 2~12 carbon atoms, the temperature of chain extension is 40 DEG C~
90℃。
In one embodiment, to have the diamines of 2~12 carbon atoms or hydramine as chain extender, the temperature of chain extension is 5 DEG C
~10 DEG C.
It in one embodiment, further include using respectively before the step of mixing chain extender with polyisocyanate trimer
The step of appropriate cosolvent dilutes polyisocyanate trimer.
S2, the obtained prepolymer of step S1 and sealer are blocked under the conditions of 60 DEG C~80 DEG C, obtain mixture,
And control in mixture-residual qualities of NCO group are less than or equal to 0.1%.
Wherein, sealer is selected from least one of amino sealer, oximido sealer and hydroxyl sealer.
In one embodiment, the sealing end time is 0.5h~5h.
S3, the solid content that cosolvent adjusts mixture is added into the mixture of step S2, it is solid obtains blocked isocyanate
Agent.
Specifically, cosolvent is added and adjusts the solid content of mixture to 75wt%~90wt%.
It should be noted that adjusting the amount of cosolvent used in the solid content to 75wt%~90wt% of mixture, refer to
The total amount of cosolvent used in whole preparation process, such as diluting polyisocyanates before carrying out chain extending reaction
The cosolvent of cleaning container is used for after the cosolvent of tripolymer and chain extender, reaction.
In one embodiment, chain extender is water, and reaction formula is as follows:
Wherein, X is the main chain section of polyisocyanate trimer, and BH is sealer.
Specifically, water and polyisocyanate trimer are subjected to chain extension under the conditions of 40 DEG C~90 DEG C, obtain urea groups pre-polymerization
Object；Then urea groups prepolymer and sealer are subjected to sealing end 0.5~5 hour under the conditions of 60 DEG C~80 DEG C, detect the remnants of NCO
Quality≤0.1% stops sealing end；Cosolvent is added and adjusts solid content to 75wt%~90wt%, filtering obtains closing isocyanic acid
Ester curing agent.
In one embodiment, chain extender is the glycol of the saturated alkyl containing 2~12 carbon atoms, the following institute of reaction formula
Show:
Wherein, X is the main chain section of polyisocyanate trimer, and R is the saturated alkyl containing 2~12 carbon atoms, and BH is
Sealer.
Specifically, chain extender glycol and polyisocyanate trimer are subjected to chain extension under the conditions of 40 DEG C~90 DEG C, obtained
Carbamate prepolymer；Then carbamate prepolymer and sealer are subjected to sealing end 0.5h under the conditions of 60 DEG C~80 DEG C
~8h, residual qualities≤0.1% of detection-NCO stop sealing end；Cosolvent is added and adjusts solid content to 75wt%~90wt%,
Filtering, obtains blocked isocyanate curing agent.
In one embodiment, chain extender is the diamines or hydramine of the saturated alkyl containing 2~12 carbon atoms, reaction formula
It is as follows:
Wherein, X is the main chain section of polyisocyanate trimer, and R is the saturated alkyl containing 2~12 carbon atoms, and X ' is
Oxygen atom or nitrogen-atoms, BH are sealer.
Specifically, with suitable cosolvent by chain extension dilution agent, and it is with appropriate cosolvent that polyisocyanate trimer is dilute
Be cooled to 5 DEG C~10 DEG C after releasing, then mix both, and carry out low temperature chain extension, obtain carbamate prepolymer and/
Or urea groups prepolymer；Then prepolymer and sealer are subjected to sealing end 0.5h~8h under the conditions of 60 DEG C~80 DEG C, detect NCO's
Residual volume≤0.1% stops sealing end；Remaining cosolvent is added and adjusts solid content to 75wt%~90wt%, filtering is sealed
Close isocyanate curing agent.
A further embodiment of this invention is to provide a kind of one-component coating, which includes above-mentioned blocked isocyanate
Curing agent uses isocyanate curing agent made from above-mentioned preparation method.
One-component coating further includes matrix resin in one of the embodiments, and matrix resin is selected from amino resins, polyester
At least one of resin and acrylic resin.
The present invention contains the one-component coating of above-mentioned blocked isocyanate curing agent, since blocked isocyanate curing agent has
There is the cross-linked structure of more crosslink sites, it can be more with tripolymer when reacting with the matrix resin in one-component coating
Site crosslinks, so as to promote the crosslink density of film.
The following are specific embodiments
- NCO residual volume is surveyed referring to " polymethylene multi-phenenyl isocyanate radical content measuring method " in GB12009.4-89
；
The measurement of solid content: it is measured under the conditions of 130 DEG C by DIN EN ISO 3251；60 minutes, initial mass
1.0g。
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) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
50% cosolvent (the mixing cosolvent of trimethylbenzene and PMA composition), IPDI tripolymer is added, while being blown into nitrogen, stirring point
15min is dissipated, then heats to 80 DEG C, stopping is blown into nitrogen, and H is added2The cosolvent of O and 30% reacts 2h, it is pre- to obtain urea groups
Aggressiveness.
(2) after the reaction was completed, 30 DEG C are cooled to, 3,5- dimethyl pyrazole is added, 20% cosolvent carries out end capping reaction,
60 DEG C of reaction temperature, time 1h is blocked, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) diatomite filtering and discharging is added to 85% in the amount of solid content of mixture obtained by detection and set-up procedure (2),
The blocked isocyanate curing agent with cross-linked structure is made.
Embodiment 2
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
50% cosolvent, HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, then heats to 80 DEG C, stop being blown into
The cosolvent of ethylene glycol and 30% is added in nitrogen, reacts 2h, obtains carbamate prepolymer.
(2) be cooled to 30 DEG C after the reaction was completed, be added 1,2,4- triazole and 20% cosolvent (trimethylbenzene/PMA) into
Row end capping reaction, blocks time 0.5h by 80 DEG C of reaction temperature, and until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is detected, adjustment amount of solid content is 75%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Embodiment 3
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
50% cosolvent (mixture of trimethylbenzene and PMA), HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, so
After be warming up to 80 DEG C, stopping is blown into nitrogen, the cosolvent (mixture of trimethylbenzene and PMA) of 1,6- hexylene glycol and 30% is added,
React 2h.
(2) it is cooled to 30 DEG C after the reaction was completed, the cosolvent (mixing of trimethylbenzene and PMA of methyl ethyl ketoxime, 20% is added
Object) end capping reaction is carried out, 60 DEG C of reaction temperature, time 4h is blocked, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is measured, adjustment amount of solid content is 90%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Embodiment 4
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
Trimethylbenzene/PMA (50%), HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, then heats to 80 DEG C, stops
It is blown into nitrogen, 1,12- dodecanediol and trimethylbenzene/PMA (30%) mixture is added, reacts 2h.
(2) it is cooled to 30 DEG C after the reaction was completed, methyl ethyl ketoxime, trimethylbenzene/PMA (20%) progress end capping reaction is added, instead
40 DEG C of temperature are answered, time 8h is blocked, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is measured, adjustment amount of solid content is 90%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Embodiment 5
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
Trimethylbenzene/PMA (20%), HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, is then cooled to 5 DEG C, stops
It is blown into nitrogen, is gradually slowly added dropwise and adds ethylenediamine and trimethylbenzene/PMA (70%) mixed solution, reacts 1h.
(2) it is cooled to 30 DEG C after the reaction was completed, methyl ethyl ketoxime, trimethylbenzene/PMA (10%) progress end capping reaction is added, instead
80 DEG C of temperature are answered, time 0.5h is blocked, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is measured, adjustment amount of solid content is 80%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Embodiment 6
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
Trimethylbenzene/PMA (20%), HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, is then cooled to 5 DEG C, stops
It is blown into nitrogen, is gradually slowly added dropwise and adds 1,6- hexamethylene diamine and trimethylbenzene/PMA (70%) mixed solution, reacts 1h.
(2) it is cooled to 30 DEG C after the reaction was completed, methyl ethyl ketoxime, trimethylbenzene/PMA (10%) progress end capping reaction is added, instead
Temperature 60 C is answered, time 4h is blocked, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is measured, adjustment amount of solid content is 75%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Embodiment 7
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
Trimethylbenzene/PMA (20%), HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, is then cooled to 5 DEG C, stops
It is blown into nitrogen, is gradually slowly added dropwise and adds 1,12- dodecyl diamines and trimethylbenzene/PMA (70%) mixed solution, reacts 1h.
(2) it is cooled to 30 DEG C after the reaction was completed, 1,2,4- triazole is added, trimethylbenzene/PMA (10%) block instead
It answers, 60 DEG C of reaction temperature, blocks time 4h, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is measured, adjustment amount of solid content is 75%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Embodiment 8
(1) reflux condensing tube, thermocouple, thermometer, nitrogen tube are installed in four round flask, under stirring,
Trimethylbenzene/PMA (20%), HDI trimer is added, while being blown into nitrogen, is dispersed with stirring 15min, is then cooled to 5 DEG C, stops
It is blown into nitrogen, is gradually slowly added dropwise and adds ethanol amine and trimethylbenzene/PMA (70%) mixed solution, reacts 1h.
(2) it is cooled to 30 DEG C after the reaction was completed, 3,5- dimethyl pyrazole is added, trimethylbenzene/PMA (10%) block anti-
It answers, 40 DEG C of reaction temperature, blocks time 8h, until measuring NCO≤0.1%, sealing end terminates, and stops reaction.
(3) amount of solid content is measured, adjustment amount of solid content is 75%, adds diatomite filtering and discharging, being made has crosslinking
The blocked isocyanate curing agent of structure.
Performance test
The blocked isocyanate curing agent that embodiment 1,4,7 is prepared carries out infrared scan respectively, obtains Fig. 1~3
Shown in map.
The measurement of film crosslink density: by lid, your a point rate is measured；Wherein, lid that divides rate test method are as follows: uses completely
Iron plate scrapes the film being fully cured from glass plate, and quality is referred to as m0, the film weighed up is placed in the mixed of methanol and acetone
It closes in liquid (volume ratio 1:1), 60 DEG C of reflux 6h, film is then placed in drying in 30 DEG C of thermostatic drying chambers and for 24 hours, claims to apply film quality
Amount is m1。
Gai Erfen rate=m1/m0× 100%.
Gai Erfen rate is bigger, indicates that film crosslink density is bigger.
According to formulation for coating material as shown in Table 2, will there is the blocked isocyanate of cross-linked structure made from Examples 1 to 8
Curing agent is configured to corresponding 1K varnish paint 1~8；350 blocked polyisocyanates curing agent of Desmodur PL is created into Cohan
Coating in contrast with preparation carries out the relevant evaluation of coating performance parameter.
Table 2
Using above-mentioned lid, you divide rate test method, and the 1K for testing above-mentioned coating 1~8 and comparison coating difference film thickness is clear
Paint the crosslink density of film；The pencil hardness (detection method reference GB/T 1730-2007) of 1K varnish film is had detected simultaneously,
Testing result is as shown in table 3.
Table 3
From 3 coating performance parameter test data of table it is found that with Cohan wound 350 blocked isocyanate of Desmodur PL solidification
Agent is compared, and the embodiment 1-8 blocked polyisocyanates curing agent obtained with cross-linked structure is able to ascend 1K varnish film
Crosslink density.
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 blocked isocyanate curing agent, which is characterized in that its raw material includes: polyisocyanate trimer, chain extender, envelope
Close agent and cosolvent；
Wherein, the polyisocyanate trimer is selected from isophorone diisocyanate trimer, hexamethylene diisocyanate
At least one of tripolymer and toluene diisocyanate trimer, the chain extender are selected from water and contain hydroxyl and/or amino
At least one of polyfunctional compound, the polyfunctional compound has 2~12 carbon atoms.
2. Blocked Isocyanate Curing Agents according to claim 1, which is characterized in that by weight percentage, former
Material include 50%~68% polyisocyanate trimer, 0.5%~10% chain extender, 5%~26% sealer and 10%~
25% cosolvent.
3. Blocked Isocyanate Curing Agents according to claim 1 or 2, which is characterized in that the chain extender be selected from water,
At least one of glycol, diamines and hydramine with 2~12 carbon atoms；And/or
The sealer is selected from least one of amino sealer, oximido sealer and hydroxyl sealer.
4. Blocked Isocyanate Curing Agents according to claim 3, which is characterized in that the polyisocyanate trimer
Selected from least one of isophorone diisocyanate trimer and hexamethylene diisocyanate trimer；And/or
The sealer is selected from least one of 3,5- dimethyl pyrazole, 1,2,4- triazole, diisopropylamine and methyl ethyl ketoxime；
And/or
The cosolvent is selected from least one of trimethylbenzene and propylene glycol methyl ether acetate.
5. blocked isocyanate curing agent according to any one of claims 1 to 4, which is characterized in that the chain extender choosing
From the saturated alkyl glycol with 2~12 carbon atoms, two hydro diamine of saturated alkyl with 2~12 carbon atoms, have 2~
At least one of the saturated alkyl glycol amine of 12 carbon atoms and water.
6. a kind of preparation method of blocked isocyanate curing agent, which comprises the following steps:
Chain extender and polyisocyanate trimer are mixed, chain extension, obtains prepolymer；Wherein, the polyisocyanate trimer
In isophorone diisocyanate trimer, hexamethylene diisocyanate trimer and toluene diisocyanate trimer
At least one, the chain extender be selected from least one of water and the polyfunctional compound containing hydroxyl and/or amino, institute
Multifunctional dough object is stated with 2~12 carbon atoms；
The prepolymer and sealer are blocked under the conditions of 60 DEG C~80 DEG C, obtain mixture；
The solid content that cosolvent adjusts the mixture is added, obtains the blocked isocyanate curing agent.
7. preparation method according to claim 6, which is characterized in that the step of sealing end controls in the mixture-
The residual qualities of NCO group are less than or equal to 0.1%.
8. preparation method according to claim 6 or 7, which is characterized in that the addition cosolvent adjusts the mixture
Solid content to 75wt%~90wt%.
9. a kind of one-component coating, which is characterized in that the one-component coating includes the described in any item envelopes of Claims 1 to 5
Close isocyanate curing agent or using blocked isocyanate curing agent made from any one of claim 6~8 preparation method.
10. one-component coating according to claim 9, which is characterized in that the one-component coating further includes matrix resin,
The matrix resin is selected from least one of amino resins, polyester resin and acrylic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910767592.2A CN110483738A (en) | 2019-08-20 | 2019-08-20 | Blocked isocyanate curing agent and preparation method thereof, one-component coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910767592.2A CN110483738A (en) | 2019-08-20 | 2019-08-20 | Blocked isocyanate curing agent and preparation method thereof, one-component coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110483738A true CN110483738A (en) | 2019-11-22 |
Family
ID=68552162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910767592.2A Pending CN110483738A (en) | 2019-08-20 | 2019-08-20 | Blocked isocyanate curing agent and preparation method thereof, one-component coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483738A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440292A (en) * | 2020-03-06 | 2020-07-24 | 长春工业大学 | Blocked isocyanate crosslinking agent and preparation method thereof |
| CN111763303A (en) * | 2020-06-24 | 2020-10-13 | 何嘉妍 | Water-based blocked polyurethane curing agent and preparation method thereof |
| CN114853970A (en) * | 2022-06-15 | 2022-08-05 | 佛山市精信汇明科技有限公司 | Closed cationic waterborne polyurethane curing agent and preparation method and application thereof |
| CN115110315A (en) * | 2022-08-03 | 2022-09-27 | 广东德美精细化工集团股份有限公司 | Bio-based water-based blocked isocyanate crosslinking agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371397A (en) * | 1999-08-30 | 2002-09-25 | 拜尔公司 | Malonic ester blocked HDI trimer with IPDA stabilization and formaldehyde stabilization |
| CN101456940A (en) * | 2008-12-31 | 2009-06-17 | 广东华润涂料有限公司 | Dissolvant type polyurethane curing agent synthetic method for producing low free toluene diisocyanate content |
| CN102816294A (en) * | 2012-08-17 | 2012-12-12 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
| CN103351460A (en) * | 2013-07-10 | 2013-10-16 | 浙江传化股份有限公司 | Preparation method of cation waterproof cross-linking agent |
| CN105671967A (en) * | 2016-03-16 | 2016-06-15 | 广州恒锦化工科技有限公司 | Durable fluoride-free waterproof agent and preparation method thereof |
| CN107686698A (en) * | 2017-09-30 | 2018-02-13 | 广东美涂士建材股份有限公司 | A kind of polyurethane woodenware priming paint that can be applied again after short interval surface drying |
| CN108424681A (en) * | 2018-03-28 | 2018-08-21 | 东莞市同丰高分子材料有限公司 | A kind of formula and synthetic method of waterborne cation high functionality Blocked Isocyanate Curing Agents |
-
2019
- 2019-08-20 CN CN201910767592.2A patent/CN110483738A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371397A (en) * | 1999-08-30 | 2002-09-25 | 拜尔公司 | Malonic ester blocked HDI trimer with IPDA stabilization and formaldehyde stabilization |
| CN101456940A (en) * | 2008-12-31 | 2009-06-17 | 广东华润涂料有限公司 | Dissolvant type polyurethane curing agent synthetic method for producing low free toluene diisocyanate content |
| CN102816294A (en) * | 2012-08-17 | 2012-12-12 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
| CN103351460A (en) * | 2013-07-10 | 2013-10-16 | 浙江传化股份有限公司 | Preparation method of cation waterproof cross-linking agent |
| CN105671967A (en) * | 2016-03-16 | 2016-06-15 | 广州恒锦化工科技有限公司 | Durable fluoride-free waterproof agent and preparation method thereof |
| CN107686698A (en) * | 2017-09-30 | 2018-02-13 | 广东美涂士建材股份有限公司 | A kind of polyurethane woodenware priming paint that can be applied again after short interval surface drying |
| CN108424681A (en) * | 2018-03-28 | 2018-08-21 | 东莞市同丰高分子材料有限公司 | A kind of formula and synthetic method of waterborne cation high functionality Blocked Isocyanate Curing Agents |
Non-Patent Citations (3)
| Title |
|---|
| 丛树枫等: "《聚氨酯涂料》", 30 September 2003, 化学工业出版社 * |
| 刘益军: "《聚氨酯原料及助剂手册》", 30 April 2005, 化学工业出版社 * |
| 李绍雄等: "《聚氨酯树脂及其应用》", 30 May 2002, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440292A (en) * | 2020-03-06 | 2020-07-24 | 长春工业大学 | Blocked isocyanate crosslinking agent and preparation method thereof |
| CN111763303A (en) * | 2020-06-24 | 2020-10-13 | 何嘉妍 | Water-based blocked polyurethane curing agent and preparation method thereof |
| CN114853970A (en) * | 2022-06-15 | 2022-08-05 | 佛山市精信汇明科技有限公司 | Closed cationic waterborne polyurethane curing agent and preparation method and application thereof |
| CN114853970B (en) * | 2022-06-15 | 2023-07-21 | 佛山市精信汇明科技有限公司 | Enclosed type cationic waterborne polyurethane curing agent and preparation method and application thereof |
| CN115110315A (en) * | 2022-08-03 | 2022-09-27 | 广东德美精细化工集团股份有限公司 | Bio-based water-based blocked isocyanate crosslinking agent and preparation method thereof |
| CN115110315B (en) * | 2022-08-03 | 2023-10-17 | 广东德美精细化工集团股份有限公司 | Bio-based water-based blocked isocyanate crosslinking agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110483738A (en) | Blocked isocyanate curing agent and preparation method thereof, one-component coating | |
| Subramani et al. | New development of polyurethane dispersion derived from blocked aromatic diisocyanate | |
| US5008363A (en) | Low temperature active aliphatic aromatic polycarbodiimides | |
| CN105308087B (en) | 1 liquid moisture curable polyurethane composition | |
| EP3063209B1 (en) | Synthesis and use of metallized polyhedral oligomeric silsequioxane catalyst compositions | |
| CN105440238B (en) | Addition compounds suitable as dispersants or antisettling agents | |
| EP0939091A1 (en) | An extremely fast curing chemical reactive coating composition, which may cure at ambient or low temperatures, with long useable pot life | |
| JPWO2019124511A1 (en) | Block isocyanate | |
| CN105683237B (en) | The thixotroping glycol composition of urethane-modified poly-isocyanurate containing dispersion | |
| US6843933B2 (en) | Blocked polyisocyanates | |
| CN108484873A (en) | A kind of use for synthetic leather high solid content polyurethane surface layer resin and preparation method thereof | |
| CN110300637A (en) | Reactive thermoplastic polyurethane based on closed isocyanates | |
| US20140242399A1 (en) | Polymer, compositions and process for preparing them | |
| CN100467511C (en) | Cyclic ketones as blocking agents | |
| CN107286312A (en) | A kind of Anionic-nonionic aqueous polyurethane dispersion and preparation method and application | |
| Li et al. | Synthesis and characterization of water-borne diisocyanate crosslinkers from methyl ethyl ketoxime/2-methylimidazole-blocked aromatic isocyanates | |
| EP2895524A1 (en) | Ethoxylate isocyanate compound and its use as emulsifier | |
| CN111320741B (en) | Water-based blocked isocyanate curing agent, preparation method thereof, water-based paint and film product | |
| EP1287054B1 (en) | Aromatic polyurethane polyol | |
| JP2000178505A (en) | One-pack thermosetting coating material and coating process therefor | |
| AU2001261642A1 (en) | Aromatic polyurethane polyol | |
| US5973097A (en) | Aldimine based coating compositions and pigment dispersions | |
| JP7287795B2 (en) | Block polyisocyanate composition, water-based coating composition and coating film | |
| US8685497B2 (en) | Liquid coating composition | |
| JPH0411593B2 (en) |
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: 20191122 |
|
| RJ01 | Rejection of invention patent application after publication |