CN105001701B - Large arch dam average molecular weight nontoxic polyurethane curing agent and its preparation method for sub-gloss varnish - Google Patents
Large arch dam average molecular weight nontoxic polyurethane curing agent and its preparation method for sub-gloss varnish Download PDFInfo
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- CN105001701B CN105001701B CN201510424566.1A CN201510424566A CN105001701B CN 105001701 B CN105001701 B CN 105001701B CN 201510424566 A CN201510424566 A CN 201510424566A CN 105001701 B CN105001701 B CN 105001701B
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Abstract
The invention belongs to the technical field of curing agent, a kind of large arch dam average molecular weight nontoxic polyurethane curing agent and its preparation method for sub-gloss varnish is disclosed.Methods described is：(1) under conditions of nitrogen is protected and is stirred, catalyst is added dropwise into the reactor equipped with solvent and toluene di-isocyanate(TDI), in 40~55 DEG C of reactions; when NCO drops to 13%~23%; cooling, adds acid polymerization inhibitor, obtains toluene diisocyanate trimer；(2) polyol is mixed with dehydrating agent, be added drop-wise in toluene di-isocyanate(TDI), reacted, cooling obtains polyurethane adducts；(3) toluene diisocyanate trimer is stirred with polyurethane adducts and mixed, thin film evaporator is separated, added retarder thinner, stir, obtain large arch dam average molecular weight nontoxic polyurethane curing agent.The curing agent molecular weight distribution is concentrated, and viscosity is low, and effective isocyanate group content is high, and with paint film drying speed after paint, good leveling property, richness is high.
Description
Technical field
The invention belongs to the technical field of curing agent, it is related to a kind of polyurethane curing agent, it is more particularly to a kind of to be used for matt
Large arch dam average molecular weight nontoxic polyurethane curing agent of paint and preparation method thereof.
Background technology
Polyurethane coating has excellent performance, is all one of most important kind in coating all the time, and wherein double
Component polyurethane coating is most widely used, and component is hydroxy-containing resin in dual-component coating, another component be containing
The curing agent of NCO.The urethane cures containing isocyanate groups are prepared using aliphatic and aromatic diisocyanate
The method of agent is widely disclosed and applied.
Toluene di-isocyanate(TDI) (TDI) can be polymerized to based on isocyanuric acid ester six-membered ring structure certainly under catalyst action
Self-aggregate mixture (claims tripolymer) more.Because tripolymer can be rapidly crosslinked with hydroxy component in resin, and itself vitrifying
Temperature is higher, and compatibility is poor, widely used in matt woodcare paint, can effectively improve hardness of paint film, adhesive force and heat
The characteristics such as stability, but it generally causes paint film richness poor.Meanwhile, usually by toluene di-isocyanate(TDI) (TDI) in
It is addition product curing agent (abbreviation addition product) with the reaction of the polyol such as trimethylolpropane (TMP), this curing agent is because of it
Pliability is good, and the features such as richness is high is widely used in light woodcare paint, but it has the disadvantage generally to do fast slower, main application
In polish lacquer.
When toluene di-isocyanate(TDI) addition product is applied in matt woodcare paint at present, general use additionally is mixed into certain ratio
The tripolymer of example achieves the goal.Tripolymer realizes that the mechanism of delustring is generally divided into two parts, and Part I is itself by tree
Flatting silica is mixed with fat, its quick-drying performance causes flatting silica to be preferably arranged in coating surface, increases extinction effect；Part II
Because tripolymer self-consistent is poor, while use ratio is relatively low, have the paint films of trimeric moieties because compatibility is poor and
The phenomenons such as curling occur in the drying process, make the uneven volatilization of solvent, causes coating surface uneven and strengthens matt effect
Really.But existing market tripolymer kind is more, performance difference is larger, and high compared with multi-product free monomer content.In addition, different batches
The application of secondary product, is influenceed by factors such as operating personnel's operating errors, causes different times paint film extinction effect different, and not
Differ larger with product molecular weight distribution, also have considerable influence to properties of product.
Find in actual applications, either toluene diisocyanate trimer or addition product, molecular weight distribution more collects
In in oligomerization, curing agent viscosity is lower, and effective NCO (NCO) content is higher, and paint film levelability is better, richness
Higher, dry speed is also very fast.Conventional chemical methods building-up process improves reaction temperature or extension reaction for reduction free monomer content
Time, cause molecule poly phenomenon in material to occur, product viscosity is so not only significantly improved, while have lost a large amount of activity
Isocyanate groups.
At present, film evaporation technique has become ripe, and Some Enterprises enter market using the method production Related product.
But due to being limited in terms of technical conditions, independent toluene diisocyanate trimer is carrying out thin film evaporation separation free monomer mistake
Cheng Zhong, the phenomenons such as crystallization, reunion occur in sample molecule and mobility is poor, it is impossible to preferably complete thin film evaporation separation.
The content of the invention
In order to overcome shortcoming and defect of the prior art, primary and foremost purpose of the invention is to provide a kind of for sub-gloss varnish
Large arch dam average molecular weight nontoxic polyurethane curing agent preparation method.The preparation method of the present invention is simple, prepared solidification
The features such as agent has large arch dam, molecular weight distribution concentration, low free monomer, for paint film quick-drying, matt, richness in coating
It is high.
It is equal another object of the present invention is to provide the large arch dam for sub-gloss varnish that is prepared by above-mentioned preparation method
Molecular weight nontoxic polyurethane curing agent.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, including following step
Suddenly：
(1) under conditions of nitrogen is protected and is stirred, it is added dropwise into the reactor equipped with solvent and toluene di-isocyanate(TDI)
Catalyst, is reacted in 40~55 DEG C, and when NCO drops to 13%~23%, cooling adds acid polymerization inhibitor, obtains toluene two
Isocyanate trimer；
(2) polyol is mixed with dehydrating agent, obtains being dehydrated polyol, polyol will be dehydrated
It is added drop-wise in toluene di-isocyanate(TDI), is then reacted 2~5 hours at 40~70 DEG C, cooling obtains polyurethane adducts；
(3) toluene diisocyanate trimer in step (1) and the polyurethane adducts in step (2) are stirred mixed
Close, obtain urethane cures agent composition；
(4) the urethane cures agent composition of step (3) is separated using thin film evaporator, it is 100 to control temperature
~200 DEG C, pressure is 10~1000Pa, and product adds retarder thinner after then separating, and it is 70%~80% to control solid content,
Stir, obtain the large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish.
Catalyst described in step (1) is triethylamine, tripropyl amine (TPA), tri-n-butyl phosphine, potassium acetate, zinc naphthenate, 2,4,6-
One or more of three (dimethylamino) phenol.
Solvent described in step (1) is more than one of ethyl acetate, butyl acetate or sec-Butyl Acetate.
Acid polymerization inhibitor is phosphoric acid or chlorobenzoyl chloride described in step (1).
The addition of catalyst described in step (1) is the 0.05%~0.55% of toluene di-isocyanate(TDI) quality；Step
(1) addition of acid polymerization inhibitor is the 0.3%~0.8% of toluene di-isocyanate(TDI) quality described in.
Toluene di-isocyanate(TDI) described in step (1) is in 2,4 toluene diisocyanate or 2,6- toluene di-isocyanate(TDI)s
One or two, preferably TDI-80.
Rate of addition described in step (1) is 40~60 drops/min；The rotating speed of stirring is 200~400r/min；The drop
The temperature of temperature is room temperature~40 DEG C, and the solvent is 1 with toluene di-isocyanate(TDI) mass ratio:(1~4).
Dehydrating agent described in step (2) is BF-5, H-581 or H-582；The consumption of the dehydrating agent is polyol
The 0.1%~0.2% of weight.
Toluene di-isocyanate(TDI) described in step (2) is in 2,4 toluene diisocyanate or 2,6- toluene di-isocyanate(TDI)s
One or two, preferably TDI-80.
The consumption of toluene di-isocyanate(TDI) described in step (2) is 3~5 times of polyol weight.
Rate of addition described in step (2) is 40~60 drops/min；The temperature of the cooling is room temperature~40 DEG C.
Polyol described in step (2) is diethylene glycol (DEG), trimethylolpropane, diethylene glycol (DEG), triethylene glycol, Ji Wusi
One or more of alcohol, PPG N210, PPG N220 and diethyl hexylene glycol.
The mass ratio of toluene diisocyanate trimer and polyurethane adducts described in step (3) is 1:(4~19).Step
Suddenly the rotating speed stirred described in (3) is 100~200r/min；The time of stirring is 30~120min；Stirring the temperature mixed is
Room temperature~50 DEG C.
Retarder thinner described in step (4) is in ethyl acetate, butyl acetate, sec-Butyl Acetate, toluene and dimethylbenzene
More than one.
The large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish is prepared by above-mentioned preparation method；
Containing admittedly for the curing agent is that 70%~80%, NCO is 11%~14%, and free TDI content is not higher than 0.4%, molecular weight point
Cloth is intensive, drying speed, with good extinction effect.The yield of the curing agent of the present invention before dilution is more than 60%.
The present invention reduces catalyst usage amount in the case where not considering free monomer content, reduces reaction temperature, simultaneously
Terminating reaction in advance, toluene di-isocyanate(TDI) it is a kind of it is gentle under conditions of can farthest carry out trimerization reaction, finally lead to
Cross thin film evaporator separation and free TDI can be separated from system, reach nontoxic level standard.Meanwhile, it is different in control toluene two
In the case of the relatively large excess of cyanate, polyol is added drop-wise to reaction system, controls reactor degree of scatter, equally may be used
To avoid the generation of polymer to the full extent.Process prepared by substep of the invention can realize toluene di-isocyanate(TDI) (TDI)
Trimerization and addition process are not interfere with each other, and ensure the molecular weight distribution collection of curing agent two parts active ingredient to the full extent
In, product viscosity is reduced, while so that NCO is farthest used.In addition, tripolymer and addition product synthesis
During have neither part nor lot in the part of reaction and can recycle, it is ensured that material makes full use of.In addition, of the invention by polyurethane addition
Thing serves as the solvent in toluene diisocyanate trimer separation process, realizes and takes off technology except toluene two is different by thin film evaporation
Monomer in cyanate tripolymer.Pass through the preparation method of the present invention, prepared toluene diisocyanate trimer and poly- ammonia
Ester addition product molecular weight is smaller and is distributed homogeneous so that curing agent mixture mobility during thin film evaporation more preferably, is more easy to
In removing monomer, large arch dam, low free polyurethane curing agent are obtained.
Compared with prior art, the invention has the advantages that：
(1) compared with existing matt curing agent, product of the present invention is solid low containing high, free monomer content, while can be direct
Use, without being compounded with other kind curing agent, and product structure, proportioning and performance are stable, reproducible.
(2) present invention catalyzes and synthesizes toluene di-isocyanate(TDI) (TDI) tripolymer using low temperature, low catalyst levels, while sharp
Polyol is in excess in toluene di-isocyanate(TDI) and prepares its addition product, the crude product that molecular weight distribution is concentrated is obtained, led to
Cross the product molecular weight distribution obtained after film evaporation technique separation to concentrate, viscosity is low, and effective isocyanate group content is high, and matches somebody with somebody
Paint film drying speed after paint, good leveling property, richness is high.
(3) toluene diisocyanate trimer refers to addition product active ingredient according to inventory and related materialization in the present invention
Mark can be calculated, and be mixed with by both certainty ratios, and can prepare different size both has tripolymer quick-drying, matt characteristic, simultaneously
There is the product for the features such as addition product richness is high again.
Embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
This.
In example below, unless stated otherwise, percentage (%) is mass percent.Free monomer content presses GB/
T18446-2009 is determined, and NCO percentage composition is determined according to HG/T2409-1992, and solid content is surveyed according to GB/2793-1995
It is fixed.
Embodiment 1
A kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, including following step
Suddenly：
(1) under nitrogen protection, 100kg toluene di-isocyanate(TDI)s (TDI-80) and 50kg ethyl acetate are added to reaction
In kettle A, stirring (rotating speed of stirring is 300r/min) is opened, temperature 55 DEG C are risen to, then by 0.15kgDMP-30 catalyst
(rate of addition is 50 drops/min) is added dropwise into reactor A, a nco value was surveyed every 1 hour, until NCO is down to 19%, cooling
To 40 DEG C, 0.45kg phosphoric acid polymerization inhibitors are added, stirs, obtains toluene di-isocyanate(TDI).
(2) under nitrogen protection, 100kg trimethylolpropanes are mixed with 0.1kgBF-5, be added drop-wise under the conditions of 60 DEG C
In reactor B equipped with 600kg toluene di-isocyanate(TDI)s (TDI-80), during dropwise addition quickly stirring (rotating speed of stirring be 600r/
Min), insulation reaction 4h after completion of dropping, obtains polyurethane adducts；
(3) reactor A and reactor B materials are transferred to reactor C, are incubated 40 DEG C, and be slowly stirred 1h (turns of stirring
Speed is 100r/min), make material dispersion uniform；
(4) product for obtaining step (3) is separated using thin film evaporator, and it is 180 DEG C to control temperature, and pressure is
50Pa, then adds butyl acetate retarder thinner by the product obtained after separation, and the solid content for controlling product is 70%, produces height
Admittedly the curing agent of nontoxic polyurethane containing average molecular weight.
The physical and chemical performance data for the polyurethane curing agent that above-mentioned preparation method is obtained are as follows：
Colourless transparent liquid, solid content 70%, nco value is 12.86%, and viscosity is 1280mPa.s (25 DEG C), free toluene
Diisocyanate content is 0.4%, and the pick-up rate of curing agent is about 65% before product dilution.
Embodiment 2
A kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, including following step
Suddenly：
(1) under nitrogen protection, 100kg toluene di-isocyanate(TDI)s (TDI-80) and 80kg ethyl acetate are added to reaction
In kettle A, stirring (rotating speed of stirring be 300r/min) is opened, temperature is risen to 55 DEG C, it is then that 0.36kgDMP-30 is same
(rate of addition is 50 drops/min) is added dropwise into reactor A in 0.18kg Tri-n-Propylamines mixed catalyst, is surveyed once every 1 hour
Nco value, until NCO is down to 17%, is cooled to 40 DEG C and adds 0.5kg phosphoric acid polymerization inhibitors, stirring is continued to employ；
(2) under nitrogen protection, after 120kg trimethylolpropanes are mixed with 0.12kgBF-5, dripped under the conditions of 60 DEG C
It is fast during dropwise addition plus (rate of addition is 50 drops/min) is arrived in the reactor B equipped with 700kg toluene di-isocyanate(TDI)s (TDI-80)
Insulation reaction 4h after speed stirring (rotating speed of stirring is 600r/min), completion of dropping, is cooled to 40 DEG C, stirring is continued to employ；
(3) reactor A and reactor B materials are transferred to reactor C, are incubated 40 DEG C, and be slowly stirred 1h (turns of stirring
Speed is 150r/min), make material dispersion uniform；
(4) product for obtaining step (3) is separated using thin film evaporator, and it is 170 DEG C to control temperature, and pressure is
80Pa, then adds butyl acetate retarder thinner by the product obtained after separation, and the solid content for controlling product is 75%, produces height
Admittedly the curing agent of nontoxic polyurethane containing average molecular weight.
The physical and chemical performance data for the polyurethane curing agent that above-mentioned preparation method is obtained are as follows：
Colourless transparent liquid, solid content 75%, nco value is 13.25%, and viscosity is 1020mPa.s (25 DEG C), free toluene
Diisocyanate content is 0.38%, and the pick-up rate of curing agent is about 63% before product dilution.
Embodiment 3
A kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, including following step
Suddenly：
(1) under nitrogen protection, 100kg toluene di-isocyanate(TDI)s (TDI-80) and 25kg ethyl acetate are added to reaction
In kettle A, stirring (rotating speed of stirring be 300r/min) is opened, temperature is risen to 55 DEG C, it is then that 0.0416kgDMP-30 is same
0.0208kg triethylamines mixed catalyst adds (rate of addition is 45 drops/min) into reactor A, is surveyed once every 1 hour
Nco value, until NCO is down to 23%, is cooled to 40 DEG C and adds 0.4kg phosphoric acid polymerization inhibitors, stirring is continued to employ；
(2) under nitrogen protection, after 140kg trimethylolpropanes are mixed with 0.14kgBF-5, dripped under the conditions of 60 DEG C
It is quick during dropwise addition plus (rate of addition is 50 drops/min) is arrived in the reactor B equipped with 650kg toluene di-isocyanate(TDI)s (TDI)
Insulation reaction 4h after stirring (rotating speed of stirring is 600r/min), completion of dropping, is cooled to 40 DEG C, stirring is continued to employ；
(3) reactor A and reactor B materials are transferred to reactor C, are incubated 40 DEG C, and be slowly stirred 1h (turns of stirring
Speed is 150r/min), make material dispersion uniform；
(4) product for obtaining step (3) is separated using thin film evaporator, and it is 160 DEG C to control temperature, and pressure is
100Pa, then adds butyl acetate retarder thinner by the product obtained after separation, and the solid content for controlling product is 70~80%,
Produce large arch dam average molecular weight nontoxic polyurethane curing agent.
The physical and chemical performance data for the polyurethane curing agent that above-mentioned preparation method is obtained are as follows：
Colourless transparent liquid, solid content 73%, nco value is 13.09%, and viscosity is 1160mPa.s (25 DEG C), free toluene
Diisocyanate content is 0.33%, and the pick-up rate of curing agent is about 77% before product dilution.
Embodiment 4
A kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, including following step
Suddenly：
(1) under nitrogen protection, 100kg toluene di-isocyanate(TDI)s (TDI-80) and 100kg ethyl acetate are added to instead
Answer in kettle A, open stirring (rotating speed of stirring be 300r/min), temperature is risen to 55 DEG C, it is then that 0.26kgDMP-30 is same
0.13kg tripropyl amine (TPA)s mixed catalyst adds (rate of addition is 50 drops/min) into reactor A, and a NCO was surveyed every 1 hour
Value, until NCO is down to 15%, is cooled to 40 DEG C and adds 0.8kg phosphoric acid polymerization inhibitors, stirring is continued to employ；
(2) under nitrogen protection, after 160kg trimethylolpropanes are mixed with 0.16kgBF-5, dripped under the conditions of 60 DEG C
It is fast during dropwise addition plus (rate of addition is 40 drops/min) is arrived in the reactor B equipped with 800kg toluene di-isocyanate(TDI)s (TDI-80)
Insulation reaction 4h after speed stirring (rotating speed of stirring is 600r/min), completion of dropping, is cooled to 40 DEG C, stirring is continued to employ；
(3) reactor A and reactor B materials are transferred to reactor C, are incubated 40 DEG C, and be slowly stirred 1h (turns of stirring
Speed is 200r/min), make material dispersion uniform；
(4) product for obtaining step (3) is separated using thin film evaporator, and it is 180 DEG C to control temperature, and pressure is
100Pa, then adds ethyl acetate retarder thinner by the product obtained after separation, and the solid content for controlling product is 70~80%,
Produce large arch dam average molecular weight nontoxic polyurethane curing agent.
The physical and chemical performance data for the polyurethane curing agent that above-mentioned preparation method is obtained are as follows：
Colourless transparent liquid, solid content 75%, nco value is 13.15%, and viscosity is 960mPa.s (25 DEG C), free toluene
Diisocyanate content is 0.37%, and the pick-up rate of curing agent is about 68% before product dilution.
Embodiment 5
A kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, including following step
Suddenly：
(1) under nitrogen protection, 100kg toluene di-isocyanate(TDI)s (TDI-80) and 35kg ethyl acetate are added to reaction
In kettle A, stirring (rotating speed of stirring be 300r/min) is opened, temperature is risen to 55 DEG C, it is then that 0.36kgDMP-30 is same
0.18kg tripropyl amine (TPA)s mixed catalyst adds (rate of addition is 50 drops/min) into reactor A, and a NCO was surveyed every 1 hour
Value, until NCO is down to 21%, is cooled to 40 DEG C and adds 0.65kg phosphoric acid polymerization inhibitors, stirring is continued to employ；
(2) under nitrogen protection, after 180kg trimethylolpropanes are mixed with 0.1kgBF-5, it is added dropwise under the conditions of 60 DEG C
(rate of addition is 40 drops/min) is arrived in the reactor B equipped with 850kg toluene di-isocyanate(TDI)s (TDI-80), quick during dropwise addition
Insulation reaction 4h after stirring (rotating speed of stirring is 600r/min), completion of dropping, is cooled to 40 DEG C, stirring is continued to employ；
(3) reactor A and reactor B materials are transferred to reactor C, are incubated 40 DEG C, and be slowly stirred 1h (turns of stirring
Speed is 200r/min), make material dispersion uniform；
(4) product for obtaining step (3) is separated using thin film evaporator, and it is 200 DEG C to control temperature, and pressure is
80Pa, then adds ethyl acetate retarder thinner by the product obtained after separation, and the solid content for controlling product is 70~80%, i.e.,
Obtain large arch dam average molecular weight nontoxic polyurethane curing agent.
The physical and chemical performance data for the polyurethane curing agent that above-mentioned preparation method is obtained are as follows：
Colourless transparent liquid, solid content 78%, nco value is 13.47%, and viscosity is 1080mPa.s (25 DEG C), free toluene
Diisocyanate content is 0.31%, and the pick-up rate of curing agent is about 79% before product dilution.
By the polyurethane curing agent of the preparation of embodiment 1,2,3, (common trimer curing agent is good to common trimer curing agent
Bao Li Chemical Groups limited company production matt tripolymer polyurethane curing agent G18M), 75% admittedly curing agent containing addition product (praise
The polyurethane curing agent G21M containing addition product admittedly of Bao Li Chemical Groups limited company production 75%) and compounding curing agent (compound
Curing agent by common trimer curing agent with 75% admittedly curing agent containing addition product constitute, wherein the content of common trimer curing agent
For the 20%) performance test in the mute varnish of 5 light splitting half, 1 the results are shown in Table.
The polyurethane curing agent performance testing index table of table 1
Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；Although with reference to foregoing each reality
Example is applied the present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each
Technical scheme described in embodiment is modified, or carries out equivalent substitution to which part or all technical characteristic；And
These modifications are replaced, and the essence of appropriate technical solution is departed from the scope of various embodiments of the present invention technical scheme.
Claims (9)
1. a kind of preparation method of large arch dam average molecular weight nontoxic polyurethane curing agent for sub-gloss varnish, it is characterised in that：Bag
Include following steps：
(1) under conditions of nitrogen is protected and is stirred, catalysis is added dropwise into the reactor equipped with solvent and toluene di-isocyanate(TDI)
Agent, is reacted in 40~55 DEG C, and mass percent is represented when NCO drops to 13%~23%, %, cooling, adds acid inhibition
Agent, obtains toluene diisocyanate trimer；
(2) polyol is mixed with dehydrating agent, obtains being dehydrated polyol, dehydration polyol is added dropwise
Into toluene di-isocyanate(TDI), then reacted 2~5 hours at 40~70 DEG C, cooling obtains polyurethane adducts；
(3) toluene diisocyanate trimer in step (1) is stirred with the polyurethane adducts in step (2) and mixed,
Obtain urethane cures agent composition；
(4) the urethane cures agent composition of step (3) is separated using thin film evaporator, it is 100~200 to control temperature
DEG C, pressure is 10~1000Pa, and product adds retarder thinner after then separating, and it is 70%~80% to control solid content, stirring
Uniformly, large arch dam average molecular weight nontoxic polyurethane curing agent is obtained；
Polyol described in step (2) is diethylene glycol (DEG), trimethylolpropane, triethylene glycol, pentaerythrite, PPG
One or more of N210, PPG N220 and diethyl hexylene glycol；
The consumption of toluene di-isocyanate(TDI) described in step (2) is 3~5 times of polyol weight；Described in step (3)
The mass ratio of toluene diisocyanate trimer and polyurethane adducts is 1:(4~19).
2. it is used for the preparation method of the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 1,
It is characterized in that：Catalyst described in step (1) be triethylamine, tripropyl amine (TPA), tri-n-butyl phosphine, potassium acetate, zinc naphthenate, 2,4,
One or more of 6- tri- (dimethylamino) phenol；
Solvent described in step (1) is one or more of ethyl acetate, butyl acetate；
Acid polymerization inhibitor is phosphoric acid or chlorobenzoyl chloride described in step (1)；
Toluene di-isocyanate(TDI) described in step (1) is one in 2,4 toluene diisocyanate or 2,6- toluene di-isocyanate(TDI)s
Plant or two kinds.
3. it is used for the preparation method of the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 1,
It is characterized in that：The addition of catalyst described in step (1) is the 0.05%~0.55% of toluene di-isocyanate(TDI) quality；
The addition of acid polymerization inhibitor is the 0.3%~0.8% of toluene di-isocyanate(TDI) quality described in step (1)；Step (1)
Described in solvent and toluene di-isocyanate(TDI) mass ratio be 1:(1~4).
4. it is used for the preparation method of the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 1,
It is characterized in that：Toluene di-isocyanate(TDI) described in step (2) is 2,4 toluene diisocyanate or 2,6- toluene diisocynates
One or both of ester；Dehydrating agent described in step (2) is BF-5, H-581 or H-582.
5. it is used for the preparation method of the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 1,
It is characterized in that：
Retarder thinner described in step (4) is one or more of ethyl acetate, butyl acetate, toluene and dimethylbenzene；
The consumption of dehydrating agent described in step (2) is the 0.1%~0.2% of polyol weight.
6. it is used for the preparation method of the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 1,
It is characterized in that：The rotating speed stirred described in step (3) is 100~200r/min；The time of stirring is 30~120min；Stirring
The temperature of mixing is room temperature~50 DEG C.
7. it is used for the preparation method of the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 1,
It is characterized in that：
Rate of addition described in step (1) is 40~60 drops/min；The rotating speed of stirring is 200~400r/min；The cooling
Temperature is room temperature~40 DEG C；
Rate of addition described in step (2) is 40~60 drops/min；The temperature of the cooling is room temperature~40 DEG C.
8. a kind of equal molecule of the large arch dam for sub-gloss varnish prepared by any one of claim 1~7 preparation method
Measure nontoxic polyurethane curing agent.
9. it is used for the large arch dam average molecular weight nontoxic polyurethane curing agent of sub-gloss varnish according to claim 8, it is characterised in that：
The solid content of the curing agent is 70%~80%；NCO is 11%~14%；Free toluene diisocyanate content is not higher than
0.4%；% represents mass percent.
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| WO2018076199A1 (en) | 2016-10-26 | 2018-05-03 | Covestro Deutschland Ag | Tdi based low-viscosity polyisocyanates with isocyanurate groups |
| WO2018076198A1 (en) | 2016-10-26 | 2018-05-03 | Covestro Deutschland Ag | Tdi based polyisocyanate mixture with a high solids content |
| CN107057034B (en) * | 2017-03-17 | 2020-02-18 | 华南理工大学 | Low-free bright toluene diisocyanate curing agent and preparation method thereof |
| JP2020525597A (en) | 2017-07-05 | 2020-08-27 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Serial dilution of polyisocyanate |
| EP3424910A1 (en) | 2017-07-05 | 2019-01-09 | Covestro Deutschland AG | Continuous dilution of polyisocyanates |
| CN112111044B (en) * | 2019-06-21 | 2021-06-29 | 万华化学集团股份有限公司 | Polyisocyanate composition and preparation method and application thereof |
| CN113087679A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Polyisocyanate curing agent with low free monomer, preparation method, coating composition and application |
| CN111454414B (en) * | 2020-05-15 | 2022-07-12 | 万华化学集团股份有限公司 | Matte polyisocyanate curing agent and preparation method and application thereof |
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| CN101717571A (en) * | 2009-10-30 | 2010-06-02 | 华南理工大学 | Method for preparing non-toxic polyurethane curing agent with high solid content |
| CN102718944B (en) * | 2012-06-07 | 2014-04-02 | 华南理工大学 | Preparation method of polyurethane trimer curing agent of low free isocyanate monomer |
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