CN105949436B - A kind of dispersible HDI-TDI mixed trimer curing agents of water and preparation method thereof - Google Patents
A kind of dispersible HDI-TDI mixed trimer curing agents of water and preparation method thereof Download PDFInfo
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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
- C08G18/795—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of mixtures of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates with aromatic 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
- C08G18/28—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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
Abstract
The invention discloses dispersible HDI TDI mixed trimer curing agents of a kind of water and preparation method thereof.The method is（1）Under nitrogen protection, diisocyanate monomer, nonionic hydrophilic modifier are put into round-bottomed flask, are warming up to 50 70 DEG C of progress insulation reactions.（2）After reacting 2 4h, catalyst for trimerization is added, continues insulation reaction, polymerization inhibitor, 0.5 1.5h of insulation reaction is added after system reaches target NCO percentage compositions.（3）Step is added in anionic hydrophilic modifying agent（2）In obtained tripolymer, continue to stir, 60 80 DEG C of insulation reactions, neutralizer is added after reacting 5 7h, stirs evenly the discharging of 0.5 1.5h postcoolings of insulation reaction.The preparation method of the present invention is simple, and prepared curing agent has the advantages that good water dispersible, excellent storage stability and paint film water resistance are good, and can be applied in aqueous polyurethane coating with bi component very well.
Description
Technical field
The invention belongs to the field of curing agent, more particularly to a kind of dispersible HDI-TDI mixed trimer curing agents of water
And preparation method thereof.
Background technology
In recent years, the development of low-carbon economy, various countries' environmental regulation perfect, and the enhancing of people's environmental consciousness promotes painting
Material industry is strided forward to the big step in " green " direction.Meanwhile as international regulations are for organic volatile in coating system（VOC）Content
Stringent limitation, force solvent based coating gradually to fade out market, promote the hair of low stain, high-performance environmentally-friendly type water paint
Exhibition, double-component waterborne polyurethane coating are even more because it combines two-component solvent borne polyurethane coating high-performance and low VOC contains
The hot spot that the advantages of amount is studied as coatings industry.Double-component waterborne polyurethane is mainly by water-based hydroxyl component and polyisocyanates
Curing agent forms, and suitable polyisocyanate curing agent is selected to have great significance dual-component polyurethane film.For double
The curing agent of component waterborne polyurethane coating is divided into two classes：Unmodified polyisocyanates and pass through hydrophilically modified polyisocyanates
Curing agent.Unmodified polyisocyanates is uniformly mixed due to more difficult with water-based hydroxyl component, in aqueous double-component system
Using being restricted.From in the early 1990s, Jacob successfully develops a kind of polyisocyanate curing agent that can be scattered in water
Afterwards, hydrophilic polyisocyanate curing agent is increasingly favored by chemist.
The hydrophilic modifying of polyisocyanate curing agent mainly realized by chemical modification, that is, internal emulsification method, there are mainly four types of
Method of modifying：It is nonionic modified, cation-modified, anion-modified, mixed and modified.It is nonionic modified generally to use polyether polyols
Alcohol carries out hydrophilic modifying, but needs in modifying process to use a large amount of polyethers could to assign polyisocyanates preferably water-dispersed
Property, this can cause the last dried coating film time long, and water resistance declines；Cation-modified is to introduce to contain in polyisocyanates
The substance of cation, then it is neutralized into salt, you can obtaining has hydrophilic polyisocyanates, but the method step is more, cost
Height, and the presence of cation can also promote reacting for-NCO and active hydrogen, the stability of system to decline；Anion-modified is with containing
The hydroxy resin of the anionic groups such as carboxyl or sulfonic group, phosphate carries out modified polyisocyanate, adds neutralizer（Such as three
Ethamine, N- methylpyrroles and N- methyl piperidines etc.）It being dispersed in water, this method 7 can delay since the pH value of its product is less than-
The reaction speed of NCO and water extend the working life of aqueous polyisocyanate curing agent, so stabilization of the pH value for curing agent
Property is affected；It is mixed and modified that aqueous polyisocyanic acid is mainly prepared using the mixed and modified method of anion and nonionic at present
Ester curing agent, this method combines the advantage that nonionic and anionic hydrophilic are modified, while compensating for both the above modification side
The shortcomings that method, but the example really used in the market is few.In conclusion how to obtain both having by internal emulsification method good
Water dispersible, bin stability water-based polyurethane curing agent be still the emphasis of research.
Water-based polyurethane curing agent includes mainly that aromatic series and aliphatic two are big in the selection to polyisocyanates at present
Class.The polyisocyanate curing agent of aromatic mainly has TDI tripolymers, TDI-TMP addition products.TDI tripolymers have function
The many merits such as degree is high, viscosity is low, high thermal stability, good corrosion resistance, as the curing agent of double-component polyurethane coating, energy
Enough make film that there are the excellent performances such as quick-drying, high rigidity, extensive use is obtained in the kinds such as quick-dry type sub-gloss varnish, polish lacquer；
TDI-TMP is also a kind of current domestic and international more common polyurethane curing agent, its comprehensive performance is strong, and curing rate is moderate, stores
It deposits and stablizes, film strength is moderate and heat resistance is all preferable, is mainly used in the priming paint of various finishing systems, anti-decaying paint and general
In terms of the application of furniture.The polyisocyanate curing agent of aliphatic category mainly has HDI biurets, HDI trimer, HDI biurets
With excellent chemical resistance and against weather（Light, resistance to chalking are protected in not yellowing）, wide in the fields such as aviation, vehicle, ship
General application；HDI trimer is not decomposed due to the presence of isocyanic acid urea ester ring at a high temperature of certain, therefore has thermal stability
Well, the advantages that wearability is good, corrosion-resistant good, is widely used in furniture, auto industry, aircraft industry frequently as polyurethane curing agent
In the fields such as sports equipment.
Aromatic and aliphatic category polyisocyanate curing agent are because respectively excellent performance is as polyurethane curing agent
And be widely used, but have certain limitation.Aromatic isocyanate is due to the presence of inductive effect ,-NCO and water
Reaction speed is very fast, and when being used as water-based polyurethane curing agent after hydrophilic modifying, water dispersible, stability are poor, together
When, generate xanthochromia since the presence of phenyl ring causes aromatic isocyanate to be easy to oxidation；Aliphatic polyisocyante curing agent-
The activity of NCO is relatively low, and the curing agent after hydrophilic modifying reacts slowly with water, helps to extend working life, but aliphatic isocyanide
Hardness of film prepared by acid esters is not good enough, and the market price is expensive, and production cost is high.
Invention content
In order to overcome shortcoming and defect in the prior art, the primary purpose of the present invention is that it is dispersible to provide a kind of water
The preparation method of HDI-TDI mixed trimer curing agents.Preparation method through the invention, you can obtain solid content 100%, NCO
For content 20 ± 0.5%, viscosity is less than 4200mPas（25℃）Water-based polyurethane curing agent.
Another object of the present invention is to provide the water-based polyurethane curing agents being prepared by the above method.
The purpose of the present invention is achieved through the following technical solutions.
A kind of dispersible HDI-TDI mixed trimer curing agents of water and preparation method thereof, include the following steps：
（1）Under nitrogen protection, first the diisocyanate monomer of certain mass, nonionic hydrophilic modifier are put into and are equipped with
Thermometer, agitating paddle 500ml drying four round flask, open stirring material stirring is uniform, then heat to 60-70
DEG C carry out insulation reaction, per hour measurement system-NCO percentage compositions.
（2）After reacting 3-4h, it is added at one time a certain amount of catalyst for trimerization, 60-70 DEG C of continuation insulation reaction, per small
When measurement system-NCO percentage compositions, be added appropriate polymerization inhibitor after system reaches target-NCO percentage compositions, 60-70 DEG C of heat preservation
React 0.5-1.5h.Unreacted diisocyanate monomer is removed by Thin film evaporation techniques.
（3）A certain amount of anionic hydrophilic modifying agent is added to step（2）In obtained tripolymer, continue to stir into
Appropriate neutralizer is added after reacting 5-6h in 70-80 DEG C of insulation reaction of row, stirs evenly insulation reaction 0.5-1.5h postcoolings and goes out
Material.
Further, step（1）Described in diisocyanate monomer be HDI and TDI mixture, wherein it is preferred that HDI
With the mixture of TDI-80, HDI:The mass ratio of TDI is（3.0-9.0）：1.
Further, step（1）Described in nonionic hydrophilic modifier be the polyethers containing ethylene oxide or propylene oxide
Polyalcohol, including polyethylene glycol（PEG）, polypropylene glycol（PPG）, poly glycol monomethyl ether, one kind in polyethylene glycol monobutyl ether
Or it is a variety of, wherein it is preferred that polyethylene glycol（PEG）, relative molecular mass 200-2000, preferably 300-700, addition two
The 3-20% of isocyanate-monomer gross mass.
Further, step（2）Described in the catalyst for trimerization that is added at one time by catalyst A and catalyst B（Mass ratio
3:1-5:1）Mixing gained, catalyst A are β-hydroxypropyl quaternary amine alkali, three normal-butyl phosphorus, 2- Hydroxyproyl Trimethyl isooctyl acid ammonium salts
With one kind in tributyltin oxide, catalyst B is DMP-30 or Mannich base 2,2- bis-（3,5- bis-（（Dimethylamino）First
Base -4- hydroxy phenyls）Propane, addition are 0. 1-0.5% of diisocyanate monomer and nonionic modified dose of gross mass.
Further, step（2）Described in polymerization inhibitor be phosphoric acid, chlorobenzoyl chloride, methyl tosylate one kind, when-
When NCO percentage composition 34-36%, it is added at one time polymerization inhibitor, additive amount is diisocyanate monomer and nonionic hydrophilic modifier
The 0.1-0.3% of gross mass.
Further, step（3）Described in anionic hydrophilic modifying agent be 2- methylol acetic acid, 2- hydroxymethylbutyrates, 3-
Hydroxyl -2,2-Dimethylpropionic acid, 2,2- dihydromethyl propionic acids（DMPA）, one kind in 2,2- dimethylolpropionic acids, wherein it is preferred that
For 2,2- dihydromethyl propionic acids, feed postition is to be added at one time, and addition is diisocyanate monomer and nonionic modified dose
The 3-5% of gross mass
Further, step（3）Described in neutralizer be sodium hydroxide, potassium hydroxide, trimethylamine, triethylamine, diethanol
Amine, N, N- dimethylethanolamines, n,N-Dimethylformamide, N, N- dimethyl pyrrolidones, N-Methyl pyrrolidone one kind
Or it is a variety of, wherein preferably triethylamine, N, N- dimethylethanolamines, N-Methyl pyrrolidone, the neutralizer quality of addition be by
According to anion-modified dose and neutralizer molar ratio 1:1 ratio is calculated.
A kind of dispersible HDI-TDI mixed trimer curing agents of water made from made as described above method.
The present invention is by HDI, TDI and nonionic modified dose of progress pre-polymerization, and adding catalyst for trimerization, to obtain HDI-TDI pre-
Aggressiveness finally adds anion-modified, neutralizer and obtains the HDI-TDI mixed trimer curing agents with water dispersible.This
On the one hand sample is done does not prepare HDI-TDI mixed trimers only with direct synthesis technique, and be wherein also added into nonionic modified
Agent carries out pre-polymerization to HDI and TDI, compared with directly using HDI trimer or TDI tripolymers to carry out hydrophilic modifying, saves
Cost.Importantly, HDI trimer, which is used alone, carries out hydrophilic modifying, since the structure of aliphatic diisocyanate causes
Its hardness of film is bad；And if be used alone TDI tripolymers carry out hydrophilic modifying, due to phenyl ring knot in aromatic diisocyanate
The presence of structure can cause the oxidizable xanthochromia of film, water resistance bad again, so the tripolymer being mixed to get using HDI-TDI
Both the advantages of having combined both HDI trimer and TDI tripolymers also compensates for the two curing agent and is applied in aqueous double-component polyurethane
The defect used in material.Simultaneously as be haved the function that before trimerization it is nonionic modified, while reaching hydrophilic modifying
Also without the degree of functionality of-NCO in reduction curing agent；On the other hand, nonionic hydrophilic modifying is used alone or anionic hydrophilic changes
The water-based polyurethane curing agent of property is not there are water dispersible is good enough, the problem of bin stability difference, obtained film there is also
The bad defect of water resistance, the present invention are prepared for aqueous polyurethane solidification using the mixed and modified method of nonionic and anion
Agent, this method combine the advantage that nonionic and anionic hydrophilic are modified, while compensating for lacking for both the above method of modifying
Point, obtained water-based polyurethane curing agent have many advantages, such as that water dispersible is good, storage is stablized, water-resistance property of coating is good.
Compared with prior art, the invention has the advantages that：
1, it is not added with any solvent in building-up process of the present invention, environmentally friendly theme is also complied with while saving cost.
2, the present invention carries out mixing trimerization using two kinds of isocyanate-monomers of HDI and TDI, is improved while reducing cost
The mechanical performances such as hardness of paint film, flexibility.
3, the present invention ensure that-NCO after hydrophilic modifying using the preparation method of first pre-polymerization poly- post-modification triplicity repeatedly
Effective functionality.
4, water-based polyurethane curing agent prepared by the method for the invention is with of light color, effective functionality is high, is not easy Huang
Become, the advantages that water dispersible is good, storage stability is good.
Specific implementation mode
Embodiment 1
（1）Under nitrogen protection, first 20g TDI-80, the diisocyanate monomer of 180g HDI, 30g PEG300 are put
Enter the drying four round flask of the 500ml equipped with thermometer, agitating paddle, unlatching stirring is uniform by material stirring, then heats up
Insulation reactions are carried out to 60 DEG C, per hour measurement system-NCO percentage compositions.
（2）After reacting 4h, 0.85g β-hydroxypropyl quaternary amine alkali and DMP-30 is added（Matter
Amount is than being 4:1）Catalyst, 60 DEG C continue insulation reaction, and measurement system-NCO percentage compositions, work as body per hour
0.4g chlorobenzoyl chlorides, insulation reaction 1h is added after reaching 34 w% of target-NCO percentage compositions in system.Unreacted diisocyanate list
Body is removed by Thin film evaporation techniques.
（3）7g DMPA are added to step（2）In obtained tripolymer, continues stirring and carry out 70 DEG C of insulation reactions, when
5.31g N, N- dimethylethanolamines are added after reacting 6h, stir evenly the discharging of insulation reaction 1h postcoolings.
HDI-TDI mixed trimer curing agents made from the present embodiment are water-white transparency liquid, solid content 100%, nco value
It is 19.69%, viscosity 3800mPas.
Embodiment 2
（1）Under nitrogen protection, first 30g TDI-80, the diisocyanate monomer of 210g HDI, 23g PEG300 are put
Enter the drying four round flask of the 500ml equipped with thermometer, agitating paddle, unlatching stirring is uniform by material stirring, then heats up
Insulation reactions are carried out to 65 DEG C, per hour measurement system-NCO percentage compositions.
（2）After reacting 3h, 0.98g β-hydroxypropyl quaternary amine alkali and Mannich base 2,2- bis- is added（3,5- bis-（（Dimethyl
Amino）Methyl -4- hydroxy phenyls）Propane（Mass ratio is 5:1）Catalyst, 65 DEG C continue insulation reaction, measure per hour
System-NCO percentage compositions, are added 0.5g chlorobenzoyl chlorides after system reaches target-NCO 35 w% of percentage composition, and 65 DEG C of heat preservations are anti-
Answer 1h.Unreacted diisocyanate monomer is removed by Thin film evaporation techniques.
（3）11g DMPA are added to step（2）In obtained tripolymer, continues stirring and carries out 75 DEG C of insulation reactions,
9.60g N-Methyl pyrrolidones are added after reacting 5h, stirs evenly the discharging of insulation reaction 1h postcoolings, it is mixed to obtain HDI-TDI
Close trimer curing agent.
HDI-TDI mixed trimer curing agents made from the present embodiment are water-white transparency liquid, solid content 100 w%, NCO
Value is 19.92 w%, viscosity 4100mPas.
Embodiment 3
（1）Under nitrogen protection, first the diisocyanate monomer of 50gTDI-80,150gHDI, 25g PEG500 are put into
Drying four round flask equipped with thermometer, the 500ml of agitating paddle, unlatching stirring is uniform by material stirring, then heats to
65 DEG C carry out insulation reactions, per hour measurement system-NCO percentage compositions.
（2）After reacting 3h, 0.90g β-hydroxypropyl quaternary amine alkali and DMP-30 is added（Mass ratio is 3:1）Catalyst, 65
DEG C continue insulation reaction, per hour measurement system-NCO percentage compositions, when system reaches target-NCO percentage compositions 35w%
0.3g chlorobenzoyl chlorides, 65 DEG C of insulation reaction 1h are added afterwards.Unreacted diisocyanate monomer is removed by Thin film evaporation techniques.
（3）The anionic hydrophilic modifying agent DMPA of 9g is added to step（2）In obtained tripolymer, continue to stir into
6.65g N-Methyl pyrrolidone neutralizers are added, after stirring evenly insulation reaction 1h in 75 DEG C of insulation reactions of row after reacting 5h
Cooling discharging obtains HDI-TDI mixed trimer curing agents.
HDI-TDI mixed trimer curing agents made from the present embodiment are water-white transparency liquid, solid content 100w%, nco value
For 20.10w%, viscosity 3620mPas.
Embodiment 4
（1）Under nitrogen protection, first 40g TDI-80, the diisocyanate monomer of 200g HDI, 10g PEG500 are put
Enter the drying four round flask of the 500ml equipped with thermometer, agitating paddle, unlatching stirring is uniform by material stirring, then heats up
Insulation reactions are carried out to 70 DEG C, per hour measurement system-NCO percentage compositions.
（2）After reacting 4h, 0.88g β-hydroxypropyl quaternary amine alkali and Mannich base 2,2- bis- is added（3,5- bis-（（Dimethyl
Amino）Methyl -4- hydroxy phenyls）Propane（Mass ratio 5:1）, 70 DEG C continue insulation reaction, per hour measurement system-NCO
0.5g chlorobenzoyl chlorides, 70 DEG C of insulation reaction 1h are added in percentage composition after system reaches target-NCO percentage composition 36w%.It is not anti-
The diisocyanate monomer answered is removed by Thin film evaporation techniques.
（3）12g DMPA are added to step（2）In obtained tripolymer, continues stirring and carries out 80 DEG C of insulation reactions,
8.86g triethylamine neutralizers are added after reacting 4h, stir evenly the discharging of insulation reaction 1h postcoolings, obtain HDI-TDI mixing three
Aggressiveness curing agent.
HDI-TDI mixed trimer curing agents made from the present embodiment are water-white transparency liquid, solid content 100w%, nco value
For 20.38w%, viscosity 4000mPas.
Embodiment 5
（1）Under nitrogen protection, first 50g TDI-80, the diisocyanate monomer of 200g HDI, 12g PEG700 are put
Enter the drying four round flask of the 500ml equipped with thermometer, agitating paddle, unlatching stirring is uniform by material stirring, then heats up
Insulation reactions are carried out to 65 DEG C, per hour measurement system-NCO percentage compositions.
（2）After reacting 3h, 0.93g β-hydroxypropyl quaternary amine alkali and DMP-30 is added（Mass ratio is 5:1）Catalyst, 65
DEG C continue insulation reaction, per hour measurement system-NCO percentage compositions, when system reaches target-NCO percentage compositions 35w%
0.3g chlorobenzoyl chlorides, 65 DEG C of insulation reaction 1h are added afterwards.Unreacted diisocyanate monomer is removed by Thin film evaporation techniques.
（3）10g DMPA are added to step（2）In obtained tripolymer, continues stirring and carries out 80 DEG C of insulation reactions,
6.65g N, N- dimethylethanolamines are added after reacting 4h, stirs evenly the discharging of insulation reaction 1h postcoolings, it is mixed to obtain HDI-TDI
Close trimer curing agent.
HDI-TDI mixed trimer curing agents made from the present embodiment are water-white transparency liquid, solid content 100w%, nco value
For 20.09w%, viscosity 4200mPas.
Embodiment 6
（1）Under nitrogen protection, first 30g TDI-80, the diisocyanate monomer of 180g HDI, 25g PEG700 are put
Enter the drying four round flask of the 500ml equipped with thermometer, agitating paddle, unlatching stirring is uniform by material stirring, then heats up
Insulation reactions are carried out to 60 DEG C, per hour measurement system-NCO percentage compositions.
（2）After reacting 4h, 0.82g β-hydroxypropyl quaternary amine alkali and Mannich base 2,2- bis- is added（3,5- bis-（（Dimethyl
Amino）Methyl -4- hydroxy phenyls）Propane（Mass ratio is 3:1）Catalyst, 60 DEG C continue insulation reaction, measure per hour
System-NCO percentage compositions, are added 0.5g chlorobenzoyl chlorides after system reaches target-NCO percentage composition 34w%, and 60 DEG C of heat preservations are anti-
Answer 1h.Unreacted diisocyanate monomer is removed by Thin film evaporation techniques.
（3）8g anionic hydrophilic modifying agent DMPA is added to step（2）In acquired tripolymer, continues stirring and carry out 70
5.28g triethylamines are added in DEG C insulation reaction after reacting 6h, stir evenly the discharging of insulation reaction 1h postcoolings, it is mixed to obtain HDI-TDI
Close trimer curing agent.
HDI-TDI mixed trimer curing agents made from the present embodiment are water-white transparency liquid, solid content 100w%, nco value
For 20.15w%, viscosity 3780mPas.
Claims (9)
1. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water, which is characterized in that including walking as follows
Suddenly：
（1）Under nitrogen protection, first diisocyanate monomer, nonionic hydrophilic modifier are put into equipped with thermometer and agitating paddle
Drying four round flask in, open stirring material stirring is uniform, then heat to 60-70 DEG C progress insulation reaction, often
Hour measurement system-NCO percentage compositions；The diisocyanate monomer is the mixture of HDI and TDI；
（2）After reacting 2-4h, it is added at one time catalyst for trimerization, continues 60-70 DEG C of insulation reaction, measures body per hour
Polymerization inhibitor, 60-70 DEG C of insulation reaction 0.5- is added in system's-NCO percentage compositions after system reaches target-NCO percentage compositions
1.5h, unreacted diisocyanate monomer are removed by Thin film evaporation techniques, obtain tripolymer；
（3）Step is added in anionic hydrophilic modifying agent（2）In gained tripolymer, continues stirring and carries out 70-80 DEG C of insulation reaction,
Neutralizer is added after reacting 5-6h, stirs evenly the discharging of insulation reaction 0.5-1.5h postcoolings, obtains HDI-TDI mixed trimers
Curing agent.
2. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（1）The diisocyanate monomer is the mixture of HDI and TDI-80；Wherein, HDI:The quality of TDI-80
Than for（3.0-9.0）：1.
3. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（1）Described in nonionic hydrophilic modifier be the polyether polyol containing ethylene oxide or propylene oxide, be added
Amount is the 3-20% of diisocyanate monomer gross mass；The polyether polyol containing ethylene oxide or propylene oxide is poly- second two
Alcohol, polypropylene glycol are one or more in poly glycol monomethyl ether and polyethylene glycol monobutyl ether.
4. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（1）Described in nonionic hydrophilic modifier be polyethylene glycol that relative molecular mass is 200-2000.
5. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（2）Described in catalyst for trimerization be catalyst A and catalyst B mixture, catalyst A be β-hydroxypropyl
Quaternary amine alkali, catalyst B are DMP-30 or Mannich base 2,2- bis-（3,5- bis-（（Dimethylamino）Methyl -4- hydroxy phenyls）Third
Alkane；The mass ratio 3 of catalyst A and catalyst B:1-5:1；The catalyst for trimerization addition be diisocyanate monomer and it is non-from
0. 1-0.5% of sub- hydrophilic modifier gross mass.
6. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（2）Described in polymerization inhibitor be phosphoric acid, chlorobenzoyl chloride and methyl tosylate in one kind；When-NCO percentages
When content 34-36w%, it is added at one time polymerization inhibitor, additive amount is diisocyanate monomer and nonionic hydrophilic modifier gross mass
0.1-0.3%.
7. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（3）Described in anionic hydrophilic modifying agent be 2- methylol acetic acid, 2- hydroxymethylbutyrates, 3- hydroxyls -2,2- bis-
Methylpropanoic acid, 2,2- dihydromethyl propionic acids and 2, one kind in 2- dimethylolpropionic acids；The anionic hydrophilic modifying agent is added
Mode is to be added at one time, and addition is the 3-6% of diisocyanate monomer and nonionic hydrophilic modifier gross mass；In described
It is sodium hydroxide, potassium hydroxide, trimethylamine, triethylamine, diethanol amine, N, N- dimethylethanolamines, N, N- dimethyl methyls with agent
Amide and N, it is one or more in N- dimethyl pyrrolidones and N-Methyl pyrrolidone；The neutralizer quality of addition be according to
Anionic hydrophilic modifying agent and neutralizer molar ratio 1:1 ratio is calculated.
8. a kind of preparation method of the dispersible HDI-TDI mixed trimer curing agents of water according to claim 1, special
Sign is：Step（3）In, the anionic hydrophilic modifying agent is 2,2- dihydromethyl propionic acids；The neutralizer be triethylamine, N,
It is one or more in N- dimethylethanolamines and N-Methyl pyrrolidone.
9. mixing three by the dispersible HDI-TDI of a kind of water that claim 1 ~ 8 any one of them preparation method is prepared
Aggressiveness curing agent.
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| CN106565937B (en) * | 2016-11-01 | 2021-06-11 | 上海氯碱化工股份有限公司 | Process for preparing controllable diphenylmethane diisocyanate trimer |
| CN107973897A (en) * | 2017-11-30 | 2018-05-01 | 华南理工大学 | A kind of dispersible mixed and modified TDI trimer curing agents of water and preparation method thereof |
| WO2020014971A1 (en) * | 2018-07-20 | 2020-01-23 | Covestro Deutschland Ag | Ionically hydrophilized polyisocyanates with improved drying |
| EP3824009B1 (en) * | 2018-07-20 | 2022-03-09 | Covestro Intellectual Property GmbH & Co. KG | Ionically hydrophilized polyisocyanates with improved drying |
| EP3599255A1 (en) | 2018-07-23 | 2020-01-29 | Covestro Deutschland AG | Ionically hydrophilized polyisocyanates with improved drying |
| CN109942791A (en) * | 2019-02-22 | 2019-06-28 | 上海稻畑精细化工有限公司 | A kind of preparation process of polyurethane curing agent |
| CN111234168B (en) * | 2020-03-05 | 2021-09-10 | 合肥安利聚氨酯新材料有限公司 | Nonionic neutralizer and preparation method thereof, waterborne polyurethane and preparation method and application thereof |
| CN113667080B (en) * | 2021-07-01 | 2022-06-14 | 华南理工大学 | HDI-TDI mixed polymer curing agent and preparation method thereof |
| CN114395109B (en) * | 2022-01-19 | 2023-06-06 | 上海稻畑精细化工有限公司 | Waterborne polyurethane curing agent and preparation method thereof |
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