CN105669947B - A kind of preparation method of non-ion aqueous HDI polyurethane curing agents - Google Patents
A kind of preparation method of non-ion aqueous HDI polyurethane curing agents Download PDFInfo
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- CN105669947B CN105669947B CN201410660541.7A CN201410660541A CN105669947B CN 105669947 B CN105669947 B CN 105669947B CN 201410660541 A CN201410660541 A CN 201410660541A CN 105669947 B CN105669947 B CN 105669947B
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Abstract
The present invention relates to a kind of preparation methods of non-ion aqueous HDI polyurethane curing agents, are mainly made of HDI trimer, low molecular polyether polyalcohol and atent solvent；A kind of non-ion aqueous HDI polyurethane curing agents produced by the present invention, aromatic-free, without gylcol ether, without alkyl phenol, have the characteristics that environmental protection, scratch resistance is good, the transparency is good, chemicals-resistant is excellent, stain resistance is strong, resistance to yellowing good；There is high rigidity, high transparency with the polyurethane paint that water-based hydroxyl component is prepared, paint film scratch resistance is good, good leveling property, the features such as richness is high, intermiscibility is good is for special curing agents such as various bi-component waterborne Polyester Paints, aqueous polyurethane paint, water-base epoxy paint, Water-borne alkyd coating, the aqueous polyurethane glue such as aqueous woodware paint, water-based industrial paint, aqueous plastic paint.
Description
Technical field
Preparation method more particularly to one kind the present invention relates to a kind of water-based polyurethane curing agent is non-ion aqueous
HDI polyurethane curing agents.
Background technology
The problem of China's reform is over 30 years, environmental degradation gradually display.By environment department and expert
Textual criticism, vehicle exhaust, also have the primary pollution sources such as airborne dust at VOC, are the main reason for causing haze weather, in primary pollution source
In, the VOC emission amount of coating and paint industry accounts for more than the 1/4 of VOC total releases；Chinese VOC annual emissions are more than 2000
Ten thousand tons, be 2 times, 3 times of European Union of the U.S..Haze, development of the whole society for green production, green product are fallen over a large area in the whole nation in the recent period
Especially pay attention to, government also puts into effect these industries one of quite stringent regulation, representative as green product, water paint
It is following developing direction, is to enjoy popular confidence；Recent water paint industry starts recovery actively, shows a piece of " Spring is very much in the air " scape
As.
Most representative waterborne two-component polyurethane coating in water paint, it is free of or containing minimal amount of organic molten
Agent, grain size are less than 0.1nm, have preferable dispersion stabilization, not only remain traditional solvent borne polyurethane coating some
Excellent performance, but also with film-forming temperature is low, strong adhesive force, wearability is good, hardness is big and chemicals-resistant, good weatherability etc.
Superior function is widely used as industrial protection, wood furniture, glassware, digital product and car paint.The poly- ammonia of aqueous dual-component
The low VOC content of the high-performance of two part solvent type polyurethane coating and water paint is combined by ester paint, becomes coating work
The research hotspot of industry.Aqueous polyurethane coating with bi component is aqueous polyalcohol by containing (- OH) base and low viscous containing (- NCO) base
Polyisocyanate curing agent composition is spent, film performance mainly forms what is determined with structure and curing agent by hydroxy resin.
At present, common polyurethane curing agent is mostly solvent type in the market, and water-based polyurethane curing agent is substantially
Offshore company is expensive such as productions such as Bayer, Rhodia, of high cost, is the main reason for water paint is difficult to promote, opens
The water-based polyurethane curing agent of hair production domesticization low cost becomes the first choice of domestic coating industry.
Invention content
The present invention is intended to provide a kind of preparation method of non-ion aqueous HDI polyurethane curing agents.
In order to solve the problems, such as techniques as described above, the present invention takes following technical scheme：The present invention relates to it is a kind of it is non-from
The preparation method of the aqueous HDI polyurethane curing agents of subtype, including following components：HDI trimer 40~85%, low molecular polyether
Polyalcohol 5~50%, atent solvent 15~25%；The HDI trimer selects NCO content to be 20.0~23.0%, be free of
The hexamethylene-diisocyanate tripolymer of solvent；The low molecular polyether polyalcohol requirement is not aqueous, selects Mr 600
~1200 polyethylene glycol, the poly glycol monomethyl ether of Mr 600~1200, Mr 800~1200 polyethylene glycol monobutyl ether, Mr
A kind of or combination of 1000 polyoxypropyleneglycol；The atent solvent requirement is not aqueous, selection diethylene glycol dimethyl ether,
Butyl, diethylene glycol ether acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate, dipropylene glycol first
Ether, dipropylene, dipropylene glycol methyl ether acetate a kind of or combination.
The present invention proposes a kind of preparation method of non-ion aqueous HDI polyurethane curing agents, and preparation process is as follows：In advance
First polyether polyol, atent solvent are carried out spare after water removal drying process；In synthesis reactor, HDI trimerizations are added in by formula ratio
After body, atent solvent dissolve by heating, low molecular polyether polyalcohol is added, is passed through N2 protections, reacts 1hr at 50~60 DEG C
Afterwards, 2~4hr of isothermal reaction is kept at 100~110 DEG C, cold filtration obtains a kind of solid content 70~80%, NCO content is
12.0~20.0%, viscosity is the non-ion aqueous HDI polyurethane curing agents of 2000~3000mPas.
Non-ion aqueous HDI polyurethane curing agents produced by the present invention, aromatic-free, without gylcol ether, be free of
Alkyl phenol；Have the characteristics that environmental protection, scratch resistance is good, the transparency is good, chemicals-resistant is excellent, stain resistance is strong, resistance to yellowing good.With water
Property the polyurethane paint prepared of hydroxy component there is high rigidity, high transparency, paint film scratch resistance is good, good leveling property, and richness is high, phase
The features such as dissolubility is good is for various bi-component waterborne Polyester Paints, water such as aqueous woodware paint, water-based industrial paint, aqueous plastic paints
The special curing agents such as property polyurethane paint, water-base epoxy paint, Water-borne alkyd coating, aqueous polyurethane glue.
Specific embodiment
Embodiment 1：
In synthesis reactor, 20 parts of diethylene glycol ether acetates dried, 68 parts of HDI trimer (NCO contents are added in
21.5%) after dissolving by heating, 12 parts of polyethylene glycol monobutyl ethers (Mr 1000) are added, are passed through N2 protections, in 50~55 DEG C of reactions
After 1hr, isothermal reaction 2.5hr are kept at 105~110 DEG C, cold filtration obtains that a kind of solid content is 80%, NCO content is
18.2%th, viscosity is the non-ion aqueous HDI polyurethane curing agents of 2500mPas.
Embodiment 2：
In synthesis reactor, 25 parts of propylene glycol methyl ether acetates dried, 65 parts of HDI trimer (NCO contents are added in
20.6%) after dissolving by heating, 10 parts of polyethylene glycol (Mr 1000) is added and are passed through N2 protections, after 60 DEG C are reacted 1hr, 100
DEG C 2.5~3hr of isothermal reaction is kept, cold filtration obtains that a kind of solid content is 75%, NCO content 17.5%, viscosity are
The non-ion aqueous HDI polyurethane curing agents of 2300mPas.
Embodiment 3：
In synthesis reactor, 20 parts of dipropylenes dried, 60 parts of HDI trimers (NCO content 21.6%) are added in
After heating for dissolving, 10 parts of poly glycol monomethyl ethers (Mr 600) and 10 parts of polyoxypropyleneglycols (Mr 1000) are added, are passed through
N2Protection after 60 DEG C are reacted 1hr, keeps 2.5~3hr of isothermal reaction, cold filtration obtains a kind of solid content and is at 100 DEG C
80%th, the non-ion aqueous HDI polyurethane curing agents that NCO content 15.6%, viscosity are 2400mPas.
Embodiment 4：
Aqueous HDI polyurethane curing agents in above-described embodiment 1,2,3 are used to prepare bi-component waterborne wood as second component
The first component formula of device polyurethane matte varnish is as follows：Water-based hydroxyl-dispersions of polyurethanes 76, dispersant 0.5, flatting silica 2, bottom
Material wetting agent 0.2, levelling agent 0.2, antifoaming agent 0.2, thickener 0.5, preservative 0.2, coalescents 3.5, PH conditioning agents 0.2,
Water 16.5；First component:Second component=100:12~20.
The basic nature of bi-component waterborne woodenware polyurethane matte varnish is used for the aqueous HDI polyurethane curing agents of the present invention
Can, it is detected according to relevant national standard, test result is as shown in table 1.
1 bi-component waterborne woodenware polyurethane matte varnish basic performance test result of table
Embodiment 5：
The preparation of aqueous dual-component industrial paint：First component formula is as follows：Water based acrylic resin 65, dispersant 1.5,
Filler and titanium dioxide 20, ground wetting agent 0.1, levelling agent 0.2, antifoaming agent 0.2, thickener 0.5, preservative 0.2, coalescents
2.6th, PH conditioning agents 0.2, water 9.5；First component:Second component=100:10~16.
The basic performance of aqueous dual-component industrial paint is used for the aqueous HDI polyurethane curing agents of the present invention, according to country
Relevant criterion is detected, and test result is as shown in table 2.
2 aqueous dual-component industrial paint basic performance test result of table
Although the present invention has described it in detail and cited embodiments, it but for those of ordinary skill in the art, shows
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (3)
1. a kind of non-ion aqueous HDI polyurethane curing agents, it is characterised in that：The non-ion aqueous HDI polyurethane
Curing agent, preparation process are as follows：In synthesis reactor, 20 parts of diethylene glycol ether acetates dried, 68 parts of HDI tri- are added in
After aggressiveness dissolves by heating, 12 parts of polyethylene glycol monobutyl ethers are added, are passed through N2Protection, after 50~55 DEG C are reacted 1hr, 105
~110 DEG C of holding isothermal reaction 2.5hr, cold filtration, obtained solid content is 80%, NCO content 18.2%, viscosity are
The non-ion aqueous HDI polyurethane curing agents of 2500mPas；
Wherein, the HDI trimer NCO content is 21.5%；The polyethylene glycol monobutyl ether is anhydrous, molecular weight Mr is
1000。
2. a kind of non-ion aqueous HDI polyurethane curing agents, it is characterised in that：The non-ion aqueous HDI polyurethane
Curing agent, preparation process are as follows：In synthesis reactor, 25 parts of propylene glycol methyl ether acetates dried, 65 parts of HDI trimerizations are added in
After body dissolves by heating, 10 parts of polyethylene glycol are added, are passed through N2Protection after 60 DEG C are reacted 1hr, keeps constant temperature anti-at 100 DEG C
2.5~3hr is answered, cold filtration, obtained solid content is 75%, NCO content 17.5%, viscosity are the described non-of 2300mPas
The aqueous HDI polyurethane curing agents of ionic；
Wherein, the HDI trimer NCO content is 20.6%；The polyethylene glycol is anhydrous, molecular weight Mr is 1000.
3. a kind of non-ion aqueous HDI polyurethane curing agents, it is characterised in that：The non-ion aqueous HDI polyurethane
Curing agent, preparation process are as follows：In synthesis reactor, 20 parts of dipropylenes dried are added in, 60 parts of HDI trimers add
After heat of solution, 10 parts of poly glycol monomethyl ethers and 10 parts of polyoxypropyleneglycols are added, are passed through N2Protection, in 60 DEG C of reactions
After 1hr, 100 DEG C keep 2.5~3hr of isothermal reaction, cold filtration, obtained solid content is 80%, NCO content 15.6%,
Viscosity is the non-ion aqueous HDI polyurethane curing agents of 2400mPas；
Wherein, the HDI trimer NCO content is 21.6%；The poly glycol monomethyl ether is anhydrous, molecular weight Mr is
600, the polyoxypropyleneglycol is anhydrous, molecular weight Mr is 1000.
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| EP3604372B1 (en) * | 2017-03-30 | 2022-12-14 | Asahi Kasei Kabushiki Kaisha | Polyisocyanate curing agent, aqueous coating composition, coating film, and coated article |
| CN107955129B (en) * | 2017-11-22 | 2020-06-23 | 辽宁恒星精细化工有限公司 | Cross-linking agent for reactive pigment imitation printing and preparation method thereof |
| CN109503810A (en) * | 2018-11-23 | 2019-03-22 | 广东聚盈化工有限公司 | A kind of non yellowing polyurethane one-component moisture solidification agent and preparation method |
| CN109824862A (en) * | 2018-12-26 | 2019-05-31 | 上海展辰涂料有限公司 | Isocyanate curing agent and preparation method thereof can be dispersed in a kind of water |
| JP7287795B2 (en) * | 2019-03-07 | 2023-06-06 | 旭化成株式会社 | Block polyisocyanate composition, water-based coating composition and coating film |
| CN109942792A (en) * | 2019-03-21 | 2019-06-28 | 华南理工大学 | A kind of phosphorous water-based polyurethane curing agent and its preparation method and application |
| CN109897153A (en) * | 2019-03-25 | 2019-06-18 | 英德市国彩精细化工有限公司 | A kind of water-dispersion type nonionic isocyanate curing agent of high crosslink density and preparation method thereof |
| CN110452362B (en) * | 2019-08-20 | 2021-11-30 | 湖南湘江关西涂料有限公司 | Water-based blocked isocyanate curing agent, preparation method thereof and water-based paint |
| CN110396163B (en) * | 2019-08-26 | 2021-11-02 | 江苏华峰超纤材料有限公司 | Water-based crosslinking agent containing carbamate structure and preparation method and application thereof |
| CN111423796B (en) * | 2020-03-31 | 2022-01-25 | 广东华润涂料有限公司 | Two-component color modifier and product made therefrom |
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