CN110408001A - A kind of preparation method of water-based polyurethane curing agent - Google Patents
A kind of preparation method of water-based polyurethane curing agent Download PDFInfo
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- 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
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- 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
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/81—Unsaturated isocyanates or isothiocyanates
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a kind of preparation methods of water-based polyurethane curing agent, belong to technical field of chemical material preparation.Long-chain fat race isocyanates is HDI class curing agent in polyurethane curing agent prepared by the present invention, it contains the preferable methylene long-chain of flexibility, so there is excellent mechanical property as the polyurethane prepared by it, local esterification can occur in amino resins and polyurethane between highly polar group such as polyether segment in polyurethane curing agent of the present invention and high density is crosslinked, form the double-deck reticular structure, improve the water resistance of polyurethane, essential oil volatility is extremely strong in oil suction rubber powder, it can be by way of being heating and curing, make essential oil that can slowly volatilize from microcapsules to release, then the microemulsified in the water phase of polyurethane curing agent, the drop of water is set to become smaller, convenient for solvent volatilization, rapid curing film forming.
Description
Technical field
The invention discloses a kind of preparation methods of water-based polyurethane curing agent, belong to technical field of chemical material preparation.
Background technique
Traditional polyurethane coating is usually solvent type, containing a large amount of volatile organic solvent, in production and use
Release a large amount of harmful volatile organic compounds.As various countries' legislations of environmental protection anticipates to the limitation and people's environmental protection of VOC
The continuous enhancing known, the exploitation and application of environment-protecting polyurethane coating are gradually valued by people.Aqueous polyurethane coating with
Water is basic medium, has the advantages that the environmental protection aspects such as nontoxic, nonflammable, energy saving, VOC content is low, is just gradually used as solvent
The substitute products of type polyurethane coating are widely used in many fields.
Polyisocyanate curing agent is the important component of polyurethane coating, mainly includes TDI, MDI, IPDI and HDI
The derivative of equal diisocyanate.Wherein, the curing agent based on HDI belongs to aliphatic firming agent, on the one hand because it is free of phenyl ring
This kind of group being easily oxidized, on the other hand because not influenced by conjugation and inductive effect, isocyanate group
Reactivity be lower than aromatic isocyanate group.In the hydrophiling research of polyisocyanates, Rudolf et al. utilizes matter
The PAPI mixture of the MDI and mass fraction 40% that measure score 60% are reacted with single functionality polyoxyethylene alcohol, and being prepared for can water
Dispersible polyisocyanate, but its working life is shorter, is no more than 3 hours.The main reason is that MDI and PAPI are aromatic series polyisocyanate
Cyanate, due to the presence of phenyl ring, so that inductive effect occurs between NCO group, the reactivity of isocyanates is greatly increased,
It is much higher than aliphatic polyisocyante with water reaction rate, after being made into paint, can reacts quickly with water and generate urea, make
The crosslink density that must be painted rises rapidly, and working life shortens.
Water-based polyurethane curing agent is that hydrophilic radical is introduced on the basis of traditional polyurethane curing agent to carry out to it
It is modified, emulsion dispersion in water is made it easier to, and keep certain stability.Common method of modifying is direct emulsion process and interior
Emulsion process.Direct emulsion process refers to that hydrophilic segment in polyurethane molecular or group content are seldom, is not enough to self-emulsifying, or
It is to be free of hydrophilic composition in its chain at all, therefore need additional emulsifier, the dispersion or newborn in water under the action of Strong shear power
Change.But dispersion liquid obtained by this method is extremely coarse, and the emulsifier being added can be free on film forming after urushoil film forming
The surface layer of object, so that film forming matter surface hydrophilic, the water resistance decline of film.Internal emulsification method is drawn during preparing polyurethane
Enter hydrophilic radical, do not need addition emulsifier, due to containing hydrophilic ingredient in polyurethane molecular skeleton, in emulsification rank
Duan Wuxu strong stirring itself can disperse to form lotion.Internal emulsification method specifically includes that cation-modified, anion-modified, non-
Ion modification and mixed and modified.Cation-modified is the substance for introducing in polyurethane curing agent and containing cation, then in
With at salt, can be obtained with hydrophilic polyurethane curing agent.Anion-modified is with containing carboxyl, sulfonic group or phosphate etc.
It is modified that the hydroxy-containing resin of anionic group carries out water-based polyurethane curing agent, add neutralizer (such as trimethylamine, triethylamine,
N- methylpyrrole etc.) it is dispersed in water.It is nonionic modified generally to carry out hydrophilic modifying using polyether polyol, but in modifying process
In need to use a large amount of polyethers and just water-based polyurethane curing agent can be made to have preferable water dispersible, it is dry that this not only results in film
The dry time is long, water resistance decline, but also can make effective-NCO percentage composition sharp fall in curing agent.
Therefore, invent that a kind of dried coating film speed is fast and the polyurethane curing agent of water-tolerant is to chemical materials technology of preparing
Field has positive effect.
Summary of the invention
Present invention mainly solves the technical issues of, be to obtain good water dispersible for existing polyurethane curing agent,
They all joined a large amount of polyethers in system, and obtained curative systems viscosity is big, and NCO content is low, excessive introducing parent
Water polyester soft segment also results in that dried coating film speed is slow, defect of poor water resistance, provides a kind of water-based polyurethane curing agent
Preparation method.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of water-based polyurethane curing agent the preparation method comprises the following steps:
Long-chain fat race isocyanates, amino resins, dimethyl silicone polymer, isophorone, triethanolamine, oil suction rubber powder is taken to set
In high speed disperser, with revolving speed 15~20min of high speed dispersion of 3000~3500r/min, adds polyethylene glycol tune and glue, obtain
To water-based polyurethane curing agent；
The preparation of long-chain fat race isocyanates are as follows:
(1) be added into the three-necked flask with dropping funel and condensing unit 70~80mL castor oil, 4~5g sodium methoxide, 5~
7mL triethanolamine, heat temperature raising, starting blender is stirred with the revolving speed of 200~300r/min, then is added into three-necked flask
Enter 40~50mL glycerol, insulated and stirred reacts 3~4h, obtains alcoholysis castor oil；
(2) hexamethylene diisocyanate is added in Xiang Shangshu three-necked flask, the reaction was continued 2~3h is cooled to 50~60 to three-necked flask
DEG C, glycerol, diethyl phosphate and maleic anhydride are successively added into three-necked flask, 3~5 parts of dibutyl tin dilaurates are dissolved in
Constant pressure funnel is poured into after acetone, is instilled in three-necked flask with the drop rate of 2~3mL/min, is heated up when being added dropwise, and is controlled
Heating rate is 3~5 DEG C/min, is warming up to 80~85 DEG C, and the reaction was continued 2~3h obtains castor oil-base isocyanates；
(3) four mouthfuls of burnings are added in castor oil-base isocyanates, trimethylolpropane, epoxidized soybean oil and dibutyl tin dilaurate
In bottle, under nitrogen protection after oil bath heating heating, start blender, with the revolving speed insulated and stirred of 300~350r/min, reaction
2~3h obtains alcoholysis product；
(4) according to parts by weight, it continues up to state and 10~15 parts of adipic acids is added in four-hole boiling flask, oil bath heating is warming up to 230
~235 DEG C, 1~2h of insulation reaction, 180~185 DEG C are cooled to, 8~10 parts of adipic anhydrides are added, are cooled to 110~120 DEG C
Afterwards, 20~30 parts of propylene glycol monomethyl ethers are added into four-hole boiling flask to be diluted, continue to be cooled to 80~85 DEG C, be added triethylamine and
Distilled water, discharging obtains long-chain fat race isocyanates after stirring 20~25min；
The preparation of oil suction rubber powder are as follows:
According to parts by weight, it takes 20~25 parts of waste yeasts to be put into supercentrifuge, is centrifuged with the revolving speed of 4000~5000r/min
10~15min discards supernatant liquor, obtains milky yeast milk, is by volume 3 ︰ 1 by milky yeast milk and tea tree ethereal oil
It is mixed to get latex oil, is washed latex oil 2~3 times with ether, the vacuum oven that set temperature is 30~45 DEG C is subsequently placed into
Middle 3~4h of drying, obtains oil suction rubber powder.
Primary raw material in the preparation of water-based polyurethane curing agent, according to parts by weight, including 40~50 parts of long-chain fat races
Isocyanates, 20~25 parts of amino resins, 5~10 parts of dimethyl silicone polymers, 8~12 parts of isophorones, 3~4 part of three ethyl alcohol
Amine, 4~5 parts of oil suction rubber powders.
The viscous control gained water-based polyurethane curing agent viscosity of polyethylene glycol tune is added in the preparation of water-based polyurethane curing agent
For 3000~3500Pa.s.
It is 50~60 DEG C that alcoholysis process temperature is controlled in the preparation of long-chain fat race isocyanates.
Castor oil-base isocyanates prepares raw material in the preparation of long-chain fat race isocyanates, according to parts by weight, including
70~80 parts of hexamethylene diisocyanates, 20~30 parts of glycerol, 10~15 parts of diethyl phosphates, 20~25 parts of maleic anhydrides, 3~5 parts
Dibutyl tin dilaurate, 35~40 parts of acetone.
The raw material of alcoholysis product is prepared in the preparation of long-chain fat race isocyanates, according to parts by weight, including 30~40
Part castor oil-base isocyanates, 10~20 parts of trimethylolpropanes, 10~12 parts of epoxidized soybean oils and 0.5~0.8 part of two laurel
Sour dibutyl tin.
Oil bath warming temperature is 180~200 DEG C when alcoholysis in the preparation of long-chain fat race isocyanates.
Triethylamine and distilled water are added in the preparation of long-chain fat race isocyanates should make to react in four-hole boiling flask in the process
Liquid pH is 8.0~8.5, can be discharged.
Milky yeast milk and tea tree ethereal oil mixed volume ratio are 3 ︰ 1 in the preparation of oil suction rubber powder.
The beneficial effects of the present invention are:
(1) present invention under the action of sodium methoxide and catalyst compounded triethanolamine with glycerol by castor oil catalyzed alcoholysis, obtain
Hexamethylene diisocyanate, diethyl phosphate, maleic anhydride, the raw materials such as glycerol, grafting are added into alcoholysis castor oil for alcoholysis castor oil
Reaction obtains castor oil-base isocyanates, and castor oil-base isocyanates, trimethylolpropane and dibutyl tin dilaurate are mixed
It closes, heating alcohol solution obtains alcoholysis product, is added adipic acid into alcoholysis product, and adipic anhydride uses propylene glycol first after insulation reaction
Ether, which is diluted, to be adjusted pH again and obtains long-chain fat race isocyanates, by long-chain fat race isocyanates, the poly- diformazan of amino resins
The raw materials such as radical siloxane, isophorone, triethanolamine, oil suction rubber powder are placed in high speed disperser, and high speed dispersion obtains aqueous poly-
Urethane curing agent, long-chain fat race isocyanates is HDI class curing agent in polyurethane curing agent prepared by the present invention, it contains soft
Pliable preferable methylene long-chain, so there is excellent mechanical property as the polyurethane prepared by it, on the one hand because it is free of
This kind of group being easily oxidized of phenyl ring, thus have good anti-yellowing property, on the other hand because not by conjugation with lure
The influence of effect is led, so therefore the reactivity of its isocyanate group (- NCO) is compared lower than aromatic isocyanate group
In aromatic polyisocyanate, it is good that polyurethane curing agent of the invention is not easy xanthochromia, dispersion stability, and polyurethane of the present invention is solid
Local esterification can occur in amino resins and polyurethane between highly polar group such as polyether segment in agent and high density is handed over
Connection, forms the double-deck reticular structure, and towards in interlayer, aqueous solvent can be gathered in double-deck netted for the hydrophilic radical of the double-deck reticular structure
Between structure, so that polyurethane curing agent outer surface is formed hydrophobic oily phase, improve the water resistance of polyurethane, also promotion polyurethane
The water dispersible of curing agent；
(2) it after amino resins and polyurethane are locally esterified in polyurethane curing agent in the present invention, is deposited at the interface of the two condensed phase
In peptide bond, peptide bond is easy hydrolysis water suction, and the outer layer for forming the double-deck reticular structure after being esterified has hydrophobic ester group, even if in tide
Humid air will not intake, so that the rate of drying of polyurethane coating film is improved, in addition, essential oil volatility pole in oil suction rubber powder
By force, it can make essential oil that can slowly volatilize from microcapsules by way of being heating and curing and release, then in polyurethane curing agent
Water phase in microemulsified, so that the drop of water is become smaller, volatilize convenient for solvent, rapid curing film forming, and the hydrophobicity of essential oil also has
Conducive to the volatilization of water in polyurethane curing agent, accelerates the drying of film in this way, bubbling will not be generated, and can drop
The reaction rate of low-NCO and water reduce the loss of-NCO in water-based system in curing agent, so that polyurethane curing agent be made to consolidate
Film surface drying time is formed when change to shorten, and is formed the water-fast paint film of high adhesion force, is had broad application prospects.
Specific embodiment
70~80mL castor oil, 4~5g sodium methoxide, 5 are added into the three-necked flask with dropping funel and condensing unit
~7mL triethanolamine is heated to 50~60 DEG C, and starting blender is stirred with the revolving speed of 200~300r/min, then to
40~50mL glycerol is added in three-necked flask, insulated and stirred reacts 3~4h, obtains alcoholysis castor oil；According to parts by weight, upwards
70~80 parts of hexamethylene diisocyanates of addition are stated in three-necked flask, the reaction was continued 2~3h is cooled to 50~60 DEG C to three-necked flask,
20~30 parts of glycerol, 10~15 parts of diethyl phosphates and 20~25 parts of maleic anhydrides are successively added into three-necked flask, by 3~5
Part dibutyl tin dilaurate pours into constant pressure funnel after being dissolved in 35~40 parts of acetone, is dripped with the drop rate of 2~3mL/min
Entering in three-necked flask, heat up when being added dropwise, control heating rate is 3~5 DEG C/min, is warming up to 80~85 DEG C, the reaction was continued 2~
3h obtains castor oil-base isocyanates；According to parts by weight, by 30~40 parts of above-mentioned castor oil-base isocyanates, 10~20 parts
Trimethylolpropane, 10~12 parts of epoxidized soybean oils and 0.5~0.8 part of dibutyl tin dilaurate are added in four-hole boiling flask, In
After oil bath heating is warming up to 180~200 DEG C under nitrogen protection, start blender, is stirred with the revolving speed heat preservation of 300~350r/min
It mixes, reacts 2~3h, obtain alcoholysis product；According to parts by weight, continue up state in four-hole boiling flask be added 10~15 parts oneself two
Acid, oil bath heating are warming up to 230~235 DEG C, 1~2h of insulation reaction, are cooled to 180~185 DEG C, and 8~10 parts of adipic acids are added
Acid anhydride after being cooled to 110~120 DEG C, is added 20~30 parts of propylene glycol monomethyl ethers into four-hole boiling flask and is diluted, continue to be cooled to 80
~85 DEG C, triethylamine and distilled water is added until reaction solution pH is 8.0~8.5 in four-hole boiling flask, discharges after stirring 20~25min
Long-chain fat race isocyanates is obtained, it is spare；According to parts by weight, 20~25 parts of waste yeasts is taken to be put into supercentrifuge, with
The revolving speed of 4000~5000r/min is centrifuged 10~15min, discards supernatant liquor, obtains milky yeast milk, by milky yeast
Cream is that 3 ︰ 1 are mixed to get latex oil with tea tree ethereal oil by volume, is washed latex oil 2~3 times with ether, is subsequently placed into setting temperature
Degree is 3~4h dry in 30~45 DEG C of vacuum oven, obtains oil suction rubber powder；According to parts by weight, take 40~50 parts it is spare
Long-chain fat race isocyanates, 20~25 parts of amino resins, 5~10 parts of dimethyl silicone polymers, 8~12 parts of isophorones, 3~
4 parts of triethanolamines, 4~5 parts of above-mentioned oil suction rubber powders are placed in high speed disperser, with the revolving speed high speed point of 3000~3500r/min
15~20min is dissipated, polyethylene glycol tune is added and sticks to 3000~3500Pa.s, obtain water-based polyurethane curing agent.
Embodiment 1
The preparation of long-chain fat race isocyanates:
70mL castor oil, 4g sodium methoxide, 5mL triethanolamine are added into the three-necked flask with dropping funel and condensing unit,
50 DEG C are heated to, starting blender is stirred with the revolving speed of 200r/min, then 40mL glycerol is added into three-necked flask,
Insulated and stirred reacts 3h, obtains alcoholysis castor oil；
According to parts by weight, 70 parts of hexamethylene diisocyanates are added in Xiang Shangshu three-necked flask, the reaction was continued 2h is dropped to three-necked flask
To 50 DEG C 20 parts of glycerol, 10 parts of diethyl phosphates and 20 parts of maleic anhydrides are successively added, by 3 parts of February in temperature into three-necked flask
Dilaurylate pours into constant pressure funnel after being dissolved in 35 parts of acetone, is instilled in three-necked flask with the drop rate of 2mL/min,
Heat up when being added dropwise, control heating rate is 3 DEG C/min, is warming up to 80 DEG C, and the reaction was continued 2h obtains castor oil-base isocyanic acid
Ester；
According to parts by weight, by 30 parts of above-mentioned castor oil-base isocyanates, 10 parts of trimethylolpropanes, 10 parts of epoxidized soybean oils and
0.5 part of dibutyl tin dilaurate is added in four-hole boiling flask, and after oil bath heating is warming up to 180 DEG C under nitrogen protection, starting is stirred
Device is mixed, with the revolving speed insulated and stirred of 300r/min, 2h is reacted, obtains alcoholysis product；
According to parts by weight, it continues up and states 10 parts of adipic acids of addition in four-hole boiling flask, oil bath heating is warming up to 230 DEG C, heat preservation
1h is reacted, 180 DEG C is cooled to, 8 parts of adipic anhydrides is added, after being cooled to 110 DEG C, 20 parts of propylene glycol first are added into four-hole boiling flask
Ether is diluted, and continues to be cooled to 80 DEG C, triethylamine and distilled water is added until reaction solution pH is 8.0 in four-hole boiling flask, stirring
Discharging obtains long-chain fat race isocyanates after 20min；
The preparation of oil suction rubber powder:
According to parts by weight, it takes 20 parts of waste yeasts to be put into supercentrifuge, 10min is centrifuged with the revolving speed of 4000r/min, is discarded
Supernatant liquor obtains milky yeast milk, is by volume that 3 ︰ 1 are mixed to get latex by milky yeast milk and tea tree ethereal oil
Oil washs latex oil 2 times with ether, is subsequently placed into dry 3h in the vacuum oven that set temperature is 30 DEG C, obtains oil suction glue
Powder；
The preparation of water-based polyurethane curing agent:
According to parts by weight, take 40 parts of spare long-chain fat race isocyanates, 20 parts of amino resins, 5 parts of dimethyl silicone polymers,
8 parts of isophorones, 3 parts of triethanolamines, 4 parts of above-mentioned oil suction rubber powders are placed in high speed disperser, with the revolving speed high speed of 3000r/min
Disperse 15min, adds polyethylene glycol tune and stick to 3000Pa.s, obtain water-based polyurethane curing agent.
Embodiment 2
The preparation of long-chain fat race isocyanates:
75mL castor oil, 4g sodium methoxide, 6mL triethanolamine are added into the three-necked flask with dropping funel and condensing unit,
55 DEG C are heated to, starting blender is stirred with the revolving speed of 250r/min, then 45mL glycerol is added into three-necked flask,
Insulated and stirred reacts 3.5h, obtains alcoholysis castor oil；
According to parts by weight, 75 parts of hexamethylene diisocyanates, the reaction was continued 2.5h, to three-necked flask are added in Xiang Shangshu three-necked flask
55 DEG C are cooled to, 25 parts of glycerol, 12 parts of diethyl phosphates and 22 parts of maleic anhydrides are successively added into three-necked flask, by 4 part two
Dibutyl tin laurate pours into constant pressure funnel after being dissolved in 37 parts of acetone, instills three-necked flask with the drop rate of 2mL/min
In, heat up when being added dropwise, control heating rate is 4 DEG C/min, is warming up to 82 DEG C, and it is different to obtain castor oil-base by the reaction was continued 2.5h
Cyanate；
According to parts by weight, by 35 parts of above-mentioned castor oil-base isocyanates, 15 parts of trimethylolpropanes, 11 parts of epoxidized soybean oils and
0.7 part of dibutyl tin dilaurate is added in four-hole boiling flask, and after oil bath heating is warming up to 190 DEG C under nitrogen protection, starting is stirred
Device is mixed, with the revolving speed insulated and stirred of 320r/min, 2.5h is reacted, obtains alcoholysis product；
According to parts by weight, it continues up and states 12 parts of adipic acids of addition in four-hole boiling flask, oil bath heating is warming up to 232 DEG C, heat preservation
1.5h is reacted, 182 DEG C is cooled to, 9 parts of adipic anhydrides is added, after being cooled to 115 DEG C, 25 parts of propylene glycol are added into four-hole boiling flask
Methyl ether is diluted, and continues to be cooled to 82 DEG C, and triethylamine and distilled water is added until reaction solution pH is 8.2 in four-hole boiling flask, stirs
Discharging obtains long-chain fat race isocyanates after mixing 22min；
The preparation of oil suction rubber powder:
According to parts by weight, it takes 22 parts of waste yeasts to be put into supercentrifuge, 12min is centrifuged with the revolving speed of 4500r/min, is discarded
Supernatant liquor obtains milky yeast milk, is by volume that 3 ︰ 1 are mixed to get latex by milky yeast milk and tea tree ethereal oil
Oil washs latex oil 2 times with ether, is subsequently placed into dry 3.5h in the vacuum oven that set temperature is 40 DEG C, obtains oil suction
Rubber powder；
The preparation of water-based polyurethane curing agent:
According to parts by weight, take 45 parts of spare long-chain fat race isocyanates, 22 parts of amino resins, 7 parts of dimethyl silicone polymers,
10 parts of isophorones, 3 parts of triethanolamines, 4 parts of above-mentioned oil suction rubber powders are placed in high speed disperser, high with the revolving speed of 3200r/min
Speed dispersion 17min, adds polyethylene glycol tune and sticks to 3200Pa.s, obtain water-based polyurethane curing agent.
Embodiment 3
The preparation of long-chain fat race isocyanates:
80mL castor oil, 5g sodium methoxide, 7mL triethanolamine are added into the three-necked flask with dropping funel and condensing unit,
60 DEG C are heated to, starting blender is stirred with the revolving speed of 300r/min, then 50mL glycerol is added into three-necked flask,
Insulated and stirred reacts 4h, obtains alcoholysis castor oil；
According to parts by weight, 80 parts of hexamethylene diisocyanates are added in Xiang Shangshu three-necked flask, the reaction was continued 3h is dropped to three-necked flask
To 60 DEG C 30 parts of glycerol, 15 parts of diethyl phosphates and 25 parts of maleic anhydrides are successively added, by 5 parts of February in temperature into three-necked flask
Dilaurylate pours into constant pressure funnel after being dissolved in 40 parts of acetone, is instilled in three-necked flask with the drop rate of 3mL/min,
Heat up when being added dropwise, control heating rate is 5 DEG C/min, is warming up to 85 DEG C, and the reaction was continued 3h obtains castor oil-base isocyanic acid
Ester；
According to parts by weight, by 40 parts of above-mentioned castor oil-base isocyanates, 20 parts of trimethylolpropanes, 12 parts of epoxidized soybean oils and
0.8 part of dibutyl tin dilaurate is added in four-hole boiling flask, and after oil bath heating is warming up to 200 DEG C under nitrogen protection, starting is stirred
Device is mixed, with the revolving speed insulated and stirred of 350r/min, 3h is reacted, obtains alcoholysis product；
According to parts by weight, it continues up and states 15 parts of adipic acids of addition in four-hole boiling flask, oil bath heating is warming up to 235 DEG C, heat preservation
2h is reacted, 185 DEG C is cooled to, 10 parts of adipic anhydrides is added, after being cooled to 120 DEG C, 30 parts of propylene glycol are added into four-hole boiling flask
Methyl ether is diluted, and continues to be cooled to 85 DEG C, and triethylamine and distilled water is added until reaction solution pH is 8.5 in four-hole boiling flask, stirs
Discharging obtains long-chain fat race isocyanates after mixing 25min；
The preparation of oil suction rubber powder:
According to parts by weight, it takes 25 parts of waste yeasts to be put into supercentrifuge, 15min is centrifuged with the revolving speed of 5000r/min, is discarded
Supernatant liquor obtains milky yeast milk, is by volume that 3 ︰ 1 are mixed to get latex by milky yeast milk and tea tree ethereal oil
Oil washs latex oil 3 times with ether, is subsequently placed into dry 4h in the vacuum oven that set temperature is 45 DEG C, obtains oil suction glue
Powder；
The preparation of water-based polyurethane curing agent:
According to parts by weight, 50 parts of spare long-chain fat race isocyanates, 25 parts of amino resins, 10 parts of polydimethylsiloxanes are taken
Alkane, 12 parts of isophorones, 4 parts of triethanolamines, 5 parts of above-mentioned oil suction rubber powders are placed in high speed disperser, with the revolving speed of 3500r/min
High speed dispersion 20min adds polyethylene glycol tune and sticks to 3500Pa.s, obtains water-based polyurethane curing agent.
Comparative example 1: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking long-chain fat race isocyanic acid
Ester.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking oil suction rubber powder.
Comparative example 3: the water-based polyurethane curing agent of Xiamen company production.
Viscosity is measured using rotational viscometer at 25 DEG C.
Nco value is detected with dibutyl amine titration.
Surface drying time test is detected by GB/T1728 standard.
Water resistance test is detected by GB/T5209 standard.
Table 1: polyurethane curing agent performance measurement result
| Detection project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Viscosity (cp) | 1430 | 1420 | 1400 | 3500 | 2900 | 2950 |
| Nco value (%) | 13.85 | 13.98 | 14.03 | 5.12 | 7.85 | 7.96 |
| Surface drying time (min) | 11 | 11 | 10 | 16 | 20 | 17 |
| Do solid work the time (h) | 17 | 16 | 16 | 20 | 23 | 20 |
| Water resistance (25 DEG C, for 24 hours) | It is unchanged | It is unchanged | It is unchanged | Obviously whiten | Slightly whiten | Slightly whiten |
In summary, water-based polyurethane curing agent viscosity of the invention is low as can be seen from Table 1, and nco value is low, surface drying time and reality
The dry time is short, and rate of drying is fast, and water-tolerant, surface is unchanged, has broad prospect of application.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of water-based polyurethane curing agent, it is characterised in that specific preparation step are as follows:
Long-chain fat race isocyanates, amino resins, dimethyl silicone polymer, isophorone, triethanolamine, oil suction rubber powder is taken to set
In high speed disperser, with revolving speed 15~20min of high speed dispersion of 3000~3500r/min, adds polyethylene glycol tune and glue, obtain
To water-based polyurethane curing agent；
The specific preparation step of long-chain fat race isocyanates are as follows:
(1) be added into the three-necked flask with dropping funel and condensing unit 70~80mL castor oil, 4~5g sodium methoxide, 5~
7mL triethanolamine, heat temperature raising, starting blender is stirred with the revolving speed of 200~300r/min, then is added into three-necked flask
Enter 40~50mL glycerol, insulated and stirred reacts 3~4h, obtains alcoholysis castor oil；
(2) hexamethylene diisocyanate is added in Xiang Shangshu three-necked flask, the reaction was continued 2~3h is cooled to 50~60 to three-necked flask
DEG C, glycerol, diethyl phosphate and maleic anhydride are successively added into three-necked flask, 3~5 parts of dibutyl tin dilaurates are dissolved in
Constant pressure funnel is poured into after acetone, is instilled in three-necked flask with the drop rate of 2~3mL/min, is heated up when being added dropwise, and is controlled
Heating rate is 3~5 DEG C/min, is warming up to 80~85 DEG C, and the reaction was continued 2~3h obtains castor oil-base isocyanates；
(3) four mouthfuls of burnings are added in castor oil-base isocyanates, trimethylolpropane, epoxidized soybean oil and dibutyl tin dilaurate
In bottle, under nitrogen protection after oil bath heating heating, start blender, with the revolving speed insulated and stirred of 300~350r/min, reaction
2~3h obtains alcoholysis product；
(4) according to parts by weight, it continues up to state and 10~15 parts of adipic acids is added in four-hole boiling flask, oil bath heating is warming up to 230
~235 DEG C, 1~2h of insulation reaction, 180~185 DEG C are cooled to, 8~10 parts of adipic anhydrides are added, are cooled to 110~120 DEG C
Afterwards, 20~30 parts of propylene glycol monomethyl ethers are added into four-hole boiling flask to be diluted, continue to be cooled to 80~85 DEG C, be added triethylamine and
Distilled water, discharging obtains long-chain fat race isocyanates after stirring 20~25min；
The specific preparation step of oil suction rubber powder are as follows:
According to parts by weight, it takes 20~25 parts of waste yeasts to be put into supercentrifuge, is centrifuged with the revolving speed of 4000~5000r/min
10~15min discards supernatant liquor, obtains milky yeast milk, is by volume 3 ︰ 1 by milky yeast milk and tea tree ethereal oil
It is mixed to get latex oil, is washed latex oil 2~3 times with ether, the vacuum oven that set temperature is 30~45 DEG C is subsequently placed into
Middle 3~4h of drying, obtains oil suction rubber powder.
2. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: described is aqueous
Primary raw material in the specific preparation step of polyurethane curing agent, according to parts by weight, including 40~50 parts of long-chain fat race isocyanic acids
Ester, 20~25 parts of amino resins, 5~10 parts of dimethyl silicone polymers, 8~12 parts of isophorones, 3~4 parts of triethanolamines, 4~5
Part oil suction rubber powder.
3. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: described is aqueous
It is 3000 that the viscous control gained water-based polyurethane curing agent viscosity of polyethylene glycol tune is added in the specific preparation step of polyurethane curing agent
~3500Pa.s.
4. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: the long-chain
Control alcoholysis process temperature is 50~60 DEG C in the specific preparation step of aliphatic isocyanates (1).
5. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: the long-chain
Castor oil-base isocyanates prepares raw material in the specific preparation step of aliphatic isocyanates (2), according to parts by weight, including 70~
80 parts of hexamethylene diisocyanates, 20~30 parts of glycerol, 10~15 parts of diethyl phosphates, 20~25 parts of maleic anhydrides, 3~5 parts of February
Dilaurylate, 35~40 parts of acetone.
6. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: the long-chain
The raw material of preparation alcoholysis product in the specific preparation step of aliphatic isocyanates (3), according to parts by weight, including 30~40 parts of castors
Sesame oil based isocyanate, 10~20 parts of trimethylolpropanes, 10~12 parts of epoxidized soybean oils and 0.5~0.8 part of tin dilaurate two
Butyl tin.
7. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: the long-chain
Oil bath warming temperature is 180~200 DEG C when alcoholysis in the specific preparation step of aliphatic isocyanates (3).
8. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: the long-chain
Triethylamine and distilled water are added in the specific preparation step of aliphatic isocyanates (4) should make reaction solution pH in four-hole boiling flask in the process
It is 8.0~8.5, can discharges.
9. a kind of preparation method of water-based polyurethane curing agent according to claim 1, it is characterised in that: the oil suction
Milky yeast milk and tea tree ethereal oil mixed volume ratio are 3 ︰ 1 in the specific preparation step of rubber powder.
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| CN111848921A (en) * | 2020-07-23 | 2020-10-30 | 深圳飞扬兴业科技有限公司 | Waterborne polyurethane resin for coating and preparation method thereof |
| CN113699829A (en) * | 2021-08-31 | 2021-11-26 | 广东肇庆福美装饰材料有限公司 | High-performance low-cycle impregnating adhesive and preparation method and use method thereof |
| CN116426113A (en) * | 2023-04-10 | 2023-07-14 | 浙江恒亿达复合材料有限公司 | High-compression-resistance fiber-reinforced polyurethane composite board and preparation method thereof |
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| CN108034342A (en) * | 2017-12-23 | 2018-05-15 | 仇颖莹 | A kind of preparation method of corrosion-resistant water-based metal baking vanish |
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| CN110724239A (en) * | 2019-11-27 | 2020-01-24 | 昆山嘉力普制版胶粘剂油墨有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
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| CN116426113A (en) * | 2023-04-10 | 2023-07-14 | 浙江恒亿达复合材料有限公司 | High-compression-resistance fiber-reinforced polyurethane composite board and preparation method thereof |
| CN116426113B (en) * | 2023-04-10 | 2024-02-27 | 浙江恒亿达复合材料有限公司 | High-compression-resistance fiber-reinforced polyurethane composite board and preparation method thereof |
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