CN109897160A - Blocked polyurethane curing agent emulsion and preparation method and application thereof - Google Patents
Blocked polyurethane curing agent emulsion and preparation method and application thereof Download PDFInfo
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- CN109897160A CN109897160A CN201910023087.7A CN201910023087A CN109897160A CN 109897160 A CN109897160 A CN 109897160A CN 201910023087 A CN201910023087 A CN 201910023087A CN 109897160 A CN109897160 A CN 109897160A
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Abstract
The invention discloses a closed polyurethane curing agent emulsion and a preparation method and application thereof. The blocked polyurethane curing agent emulsion is prepared by the following preparation method: a) preparing a polyisocyanate prepolymer containing sulfonic acid groups; b) preparing a blocked polyisocyanate prepolymer; c) and preparing the blocked polyurethane curing agent emulsion. Also discloses the application of the blocked polyurethane curing agent emulsion. The blocked polyurethane curing agent emulsion of the invention exists in the form of aqueous emulsion and can be independently stored for a long time. The emulsion has no organic solvent, high solid content and high NCO content, can be directly diluted by water, can be directly mixed with water-based resin containing active hydrogen and then stored for a long time, and the prepared water-based baking varnish and water-based high-temperature adhesive are convenient to use, and endow the product with good water resistance and high strength.
Description
Technical field
The present invention relates to a kind of urethane cures agent material, in particular to a kind of blocked polyurethane curing agent lotion and its
Preparation method and application.
Background technique
Currently, the scientific and technical personnel of polyurethane field are carrying out the research of water-based polyurethane curing agent in high gear,
Some patent documents are disclosed, some new products occurs and enters informal selling, to the original of several trans-corporations such as Japan, Germany
Kind plays the supplement of diversification application.But existing water-based polyurethane curing agent is taken a broad view of, all there is one for application
Common problem must be added water high speed dispersion to emulsify before the use, then be mixed with the resin of hydroxyl, this, which gives, uses band
It is inconvenient to come, and the pot life of the urethane cures agent emulsion after emulsification is short, in the reactive NCO group and lotion contained by it
Water react, can constantly consume effective ingredient, cause the waste of raw material.
Research for watersoluble closed type polyurethane curing agent needed for aqueous high temperature baking vanish and aqueous high-temp glue, in recent years
Also it has made some progress, discloses partial monopoly document, a small amount of Test market new products occur, change imported product and monopolize water
The situation in property blocked curing agent market.The advantages of watersoluble closed type polyurethane curing agent emulsion, is prominent, because of its activity-NCO base
Group has been closed, and can coexist steadily in the long term with the water-base resin with reactive hydrogen at normal temperature, and when heating releases-NCO, and aqueous
Hydroxyl, carboxyl, amino groups react to form cross-linked structure on molecular resin chain；It, which also has, does not have the ionic of resin system
There is the advantages of strict demand, can both be used in anion, cationic system, can also be used in nonionic system.But
It is the of less types of the watersoluble closed type polyurethane curing agent emulsion sold currently on the market, and the solid content of product compares
It is low, whether imported product or homemade goods, solid content all 40% hereinafter, NCO content 6% hereinafter, this brings system
Cause the increase of sheet, packing cost, transportation cost and use cost.In addition, watersoluble closed type polyurethane curing agent also,
Product is not with water emulsion but exists with organic solution form that there is only the environmental issues that solvent bank comes for this, and
It also needs before the use plus water emulsification is at dispersion liquid.Adding the number of water also has stringenter limitation, and water has been added and can be demulsified,
Add and lacked and emulsified bad, the user of emulsifying machine, does not stir by hand, and dispersion is uneven, is easy to produce particle；Even if machine
Device stirs the curing agent emulsion to be formed and must also be mixed into emulsion resin at once, otherwise places a period of time (general several hours
To more than 20 a hours) it will be layered, great inconvenience is brought to user's use.
CN101649036A discloses a kind of polyisocyanate curing agent, is with diisocyanate monomer and dihydric alcohol and three
The mixture of first alcohol reacts in cosolvent, generates branch polyisocyanates, again closes NCO after hydrophilic chain extension, be neutralized into
Solid content is diluted to for 50~70% watersoluble closed type polyisocyanate curing agent, in the product with viscosity reduction protection solvent after salt
There are 30~50% organic solvents, cannot directly mix with resin emulsion, it is necessary to which before the use plus water emulsification is at dispersion liquid
It could be added in resin emulsion.CN107793544A discloses a kind of environment-friendly polyurethane curing agent, is with small molecule sulfonate
Make hydrophilic radical, with polyisocyanates and diisocyanate prepolymer at the polyisocyanate prepolymers containing sulfonic acid group, then
By the activity in prepolymer-NCO group closing, Waterborne Blocked Polyurethane curing agent is made, which also contains 25~50%
Organic solvent, be also required to before use plus water emulsification could be mixed at dispersion liquid with resin emulsion.
The disclosed method for preparing watersoluble closed isocyanate curing agent of existing patent document is very limited, the research to it
It is deep not enough, and there are following two technical problem needs to overcome: first is that the solid content of lotion is low and higher cost, second is that with
Solution form, which exists, brings inconvenient for use and environmental issue to user.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, the purpose of the present invention is to provide a kind of blocked polyurethane curing agents
Lotion and its preparation method and application, this blocked polyurethane curing agent lotion have high solids content, high NCO%, without organic
The advantages of solvent, and can store for a long time at room temperature.
In order to realize the above object, the technical solution used in the present invention is:
A kind of preparation method of blocked polyurethane curing agent lotion, comprising the following steps:
A) prepare the polyisocyanate prepolymers containing sulfonic acid group: in organic solvent, with small molecule sulfonate dihydric alcohol,
Polyisocyanate prepolymers and diisocyanate are raw material, or with small molecule sulfonate dihydric alcohol, diisocyanate and ternary
Alcohol is raw material, prepares the polyisocyanate prepolymers containing sulfonic acid group；
B) prepare blocked polyisocyanate prepolymer: by containing sulfonic acid group polyisocyanate prepolymers and sealer it is anti-
It answers, closes terminal isocyanate group, obtain blocked polyisocyanate prepolymer；
C) it prepares blocked polyurethane curing agent lotion: blocked polyisocyanate prepolymer is mixed with emulsion adjuvant,
Emulsification is added water, organic solvent is removed, obtains blocked polyurethane curing agent lotion.
Preferably, in the preparation method of this blocked polyurethane curing agent lotion, step a) is prepared containing sulfonic acid group
Polyisocyanate prepolymers are any one of following methods:
Method one:
S1: small molecule sulfonate dihydric alcohol is dissolved in organic solvent, and polyisocyanate prepolymers are added and are reacted；
S2: diisocyanate is added and is reacted, the polyisocyanate prepolymers containing sulfonic acid group are obtained；
Method two:
S1: small molecule sulfonate dihydric alcohol is dissolved in organic solvent, and diisocyanate is added and is reacted；
S2: trihydroxylic alcohol is added and is reacted, the polyisocyanate prepolymers containing sulfonic acid group are obtained.
Preferably, in the preparation method step a) of this blocked polyurethane curing agent lotion, small molecule sulfonate binary
Alcohol molecular weight is 350~1000；It is further preferred that small molecule sulfonate dihydric alcohol is the sulfonic acid that molecular weight is 350~1000
One of salt dihydric alcohol or the dispersible sulfonated polyester dihydric alcohol of water are a variety of.
Preferably, in the preparation method step a) of this blocked polyurethane curing agent lotion, polyisocyanate prepolymers
For the prepolymer of diisocyanate and trihydroxylic alcohol, TDI tripolymer, MDI tripolymer, HDI trimer, IPDI tripolymer, HDI contracting two
At least one of urea, PAPI.
Preferably, in the preparation method step a) of this blocked polyurethane curing agent lotion, diisocyanate MDI,
At least one of HMDI, TDI, HDI, IPDI.
Preferably, in the preparation method step a) of this blocked polyurethane curing agent lotion, trihydroxylic alcohol is trihydroxy methyl
At least one of propane, trimethylolethane, glycerol, 1,2,6- hexanetriol.
Preferably, in the preparation method step a) of this blocked polyurethane curing agent lotion, organic solvent is that esters are molten
At least one of agent, ketones solvent；It is further preferred that organic solvent is that boiling point is molten lower than 100 DEG C of esters and/or ketone
Agent；Still further preferably, organic solvent be acetone, butanone, ethyl acetate, isopropyl acetate, methyl acetate, propyl acetate,
At least one of methyl isopropyl Ketone, glycol dimethyl ether.
It further illustrates, preferably boiling point is in order to rear in 100 DEG C of esters below and/or the purpose of ketones solvent
Continue and be easy removing solvent when room temperature or 50 DEG C or less vacuumize, the moisture in lotion is unlikely to remove together.
Preferably, in the method one of the preparation method step a) of this blocked polyurethane curing agent lotion, polyisocyanic acid
The isocyanate group of ester prepolymer and the isocyanate group molar ratio of diisocyanate are 1:(0~0.8)；Total isocyanate group with
The hydroxyl molar ratio of small molecule sulfonate dihydric alcohol is (1.5~8): 1.
Preferably, in the method one of the preparation method step a) of this blocked polyurethane curing agent lotion, the temperature of reaction
Degree is 40 DEG C~100 DEG C, stops reaction when the NCO percentage composition decline for detecting reactant tends towards stability.
It further illustrates, in the method one of preparation method step a), by small molecule sulfonate dihydric alcohol elder generation and polyisocyanate
Cyanate prepolymer reacts a period of time at low temperature, adds diisocyanate one and reacts, the reason is that polyisocyanates
The activity of prepolymer is lower than diisocyanate, in order to make hydrophilic sulfonic acid group be more evenly distributed.
Preferably, in two S1 of method of the preparation method step a) of this blocked polyurethane curing agent lotion, small molecule
The molar ratio of sulfonate dihydric alcohol and diisocyanate is (0.05~0.2): 1.
Preferably, in two S1 of method of the preparation method step a) of this blocked polyurethane curing agent lotion, reaction tool
Body is that 1h~2h is reacted at 45 DEG C~70 DEG C, and 2h~10h is then reacted at 70 DEG C~100 DEG C.
Preferably, in two S2 of method of the preparation method step a) of this blocked polyurethane curing agent lotion, trihydroxylic alcohol
Hydroxyl reacted with S1 after residue NCO molar ratio be (0.4~0.5): 1.
Preferably, two S2 of method of the preparation method step a) of this blocked polyurethane curing agent lotion will be specifically, will
Reaction temperature control is 50 DEG C~70 DEG C, divides 3~8 times in 2h~3h and trihydroxylic alcohol is added portionwise, then at 60 DEG C~100 DEG C
Reaction, the NCO percentage composition for starting to survey reactant after 3h decline stopping reaction when tending towards stability.
Preferably, in the preparation method step b) of this blocked polyurethane curing agent lotion, sealer is hydrogeneous chemical combination
Object；It is further preferred that sealer be methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketoxime, acetoxime,
Methyl-isobutyl oxime, imidazoles, 2- methylpyrazole, 3,5- dimethyl pyrazole, 3- methyl -5- ethylpyrazol, 3- ethyl -5- propyl pyrrole
At least one of azoles, acetylacetone,2,4-pentanedione, ethyl acetoacetate, diethyl malonate, epsilon-caprolactams, phenol, catechol；Into
One step is preferred, and sealer is methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, methyl ethyl ketoxime, acetoxime, methyl-isobutyl oxime, 2- first
Base pyrazoles, 3,5- dimethyl pyrazole, 3- methyl -5- ethylpyrazol, 3- ethyl -5- propylpyrazol, epsilon-caprolactams, phenol, neighbour
At least one of benzenediol.
Preferably, in the preparation method step b) of this blocked polyurethane curing agent lotion, sealer hydrogen-containing compound
Reactive hydrogen with the molar ratio of terminal isocyanate group being closed be (1.02~1.2): 1.
Preferably, the preparation method step b) of this blocked polyurethane curing agent lotion specifically: adjust in reaction kettle
Temperature is 20~70 DEG C, adds hydrogen-containing compound in batches in 1~3 hour, is then 20 DEG C~80 DEG C reactions, reaction in temperature
Time be 1h~5h.
Preferably, in the preparation method step c) of this blocked polyurethane curing agent lotion, emulsion adjuvant is halogenated hydrocarbons
Solvent；It is further preferred that emulsion adjuvant is halogenated hydrocarbon solvent not soluble in water；Still further preferably, emulsion adjuvant is not
It is dissolved in the chlorinated hydrocarbon solvent of water；Still more preferably, this emulsion adjuvant is low boiling point intensive polar solvent not soluble in water, choosing
From at least one of methylene chloride, dichloroethanes, dichloroethylene, trichloro ethylene.
Preferably, in the preparation method step c) of this blocked polyurethane curing agent lotion, the additional amount of emulsion adjuvant
It is the 10%~50% of blocked polyisocyanate prepolymer solids gross mass.
Preferably, in the preparation method step c) of this blocked polyurethane curing agent lotion, the temperature of water emulsification is added to be
20 DEG C~40 DEG C.
Preferably, in the preparation method step c) of this blocked polyurethane curing agent lotion, the speed of agitator of emulsification is not
Less than 1000 revs/min；It is further preferred that the speed of agitator of emulsification is 1000 revs/min~1500 revs/min.
Preferably, in the preparation method step c) of this blocked polyurethane curing agent lotion, the time of emulsification is 5min
~20min.
Preferably, in the preparation method step c) of this blocked polyurethane curing agent lotion, the side of organic solvent is removed
Method is vacuum distillation.
It is further preferred that the preparation method of this blocked polyurethane curing agent lotion specifically includes the following steps:
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
Method 1
S1: in the reactor, small molecule sulfonate dihydric alcohol being dissolved in organic solvent, and polyisocyanates pre-polymerization is added
Object carries out heating reaction；
S2: diisocyanate is added, carries out heating reaction, obtains the polyisocyanate prepolymers containing sulfonic acid group；
Method 2
S1: in the reactor, small molecule sulfonate dihydric alcohol being dissolved in organic solvent, and diisocyanate is added and is added
Thermal response；
S2: trihydroxylic alcohol is added, carries out heating reaction, obtains the polyisocyanate prepolymers containing sulfonic acid group；
B) blocked polyisocyanate prepolymer is prepared
In the reactor, sealer is added to carry out heating with the polyisocyanate prepolymers containing sulfonic acid group and react, obtains
Blocked polyisocyanate prepolymer；
C) blocked polyurethane curing agent lotion is prepared
In the reactor, emulsion adjuvant is added to mix with blocked polyisocyanate prepolymer, adds water and is emulsified,
Vacuum removal organic solvent, discharging, obtains blocked polyurethane curing agent lotion.
It is further preferred that the time that sealer is added in step b) is 1h~3h, adding the time reacted after sealer is
1h~5h.
It is further preferred that the time that water is added in step c) is 10min~30min, add continue after water to stir 5min~
20min is emulsified.
It is further preferred that the time of step c) vacuum removal organic solvent is 1h~3h；Vacuum removal organic solvent
Temperature is room temperature~50 DEG C；The vacuum degree of vacuum removal organic solvent is 0.01MPa~0.09MPa.
A kind of blocked polyurethane curing agent lotion is made by above-mentioned preparation method.
The present invention also provides this blocked polyurethane curing agent lotions to prepare aqueous polyurethane baking vanish and/or aqueous
Application in polyurethane high-temp glue.
Preferably, this application is specifically: by blocked polyurethane curing agent lotion and waterborne polyurethane resin/aqueous third
Water-based stoving paint or aqueous high-temp glue is respectively prepared in olefin(e) acid resin；Either by blocked polyurethane curing agent lotion and aqueous amino
Water-based stoving paint is made in resin/aqueous alkide resin.
The beneficial effects of the present invention are:
Blocked polyurethane curing agent lotion of the invention is existed with water emulsion, can individually be stored for a long time.It should
Organic solvent-free in lotion, solid content are high, and NCO content is high, can directly be diluted with water, can directly with the water-base resin containing reactive hydrogen
It is stored for a long time after mixing, manufactured water-based stoving paint and aqueous high-temp glue are easy to use, and water-tolerant, the intensity for assigning product are high.
Compared with prior art, the present invention has the advantage that
1) present invention selection dichloroethanes, methylene chloride, dichloroethylene, trichloro ethylene make watersoluble closed type polyurethane solidification
The emulsion adjuvant of agent solves high concentration though emulsion adjuvant, plays the role of the formation of stability of emulsion conclusive
The technology of preparing of blocked polyurethane curing agent lotion and the stability problem individually stored.
2) blocked polyurethane curing agent lotion of the invention provides product with water emulsion, does not need before use
Emulsification can be mixed with water-base resin or emulsion glue, and mixed lotion can be stored for a long time, bring to user easy to use, and be protected
The quality of mixed emulsion is demonstrate,proved.
3) blocked polyurethane curing agent lotion of the invention is applied widely, does not have to the ionic of auxiliary resin system
It is strict with, can both use, and can also be used in nonionic system in anion, cationic system.
4) solid content of product of the present invention is high, effective functional group content is high.It is poly- for the enclosed type prepared with HDI, PAPI
The solid content of urethane curing agent emulsion can reach 55% or more, NCO% and reach 9% or more；For with MDI, TDI, IPDI preparation
The solid content of blocked polyurethane curing agent lotion can reach 50% or more, NCO% and reach 6% or more.Of the invention is effective
Component content is high, and the additional amount in water-base resin is relatively low to assign product higher strength character, therefore curing agent
Utilization rate is relatively high, advantageously reduces user cost, improves the strength character of solidfied material.
5) low boiling point solvent of product of the present invention during the preparation process has been extracted, and is free of organic solvent, is real ring
Guarantor's type lotion；And preferably boiling point is in 100 DEG C of solvents below, can save energy in room temperature or 50 DEG C or less cryogenic vacuum removing
Source.
6) raw material sources of the present invention are convenient, and preparation process is simple.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.It is small used in embodiment
Molecule sulfonate dihydric alcohol can refer to the method preparation of CN107793544A embodiment 1, and also the dispersible sulfonation of commercially available water is poly-
Ester dihydric alcohol.Other raw materials unless otherwise specified, can be obtained from routine business approach.
Detection method in embodiment is described as follows:
1, detection viscosity by national standard " the measurement list cylinder rotary viscosimeter method of GB/T2794-2013 adhesive viscosity " into
Row.
2, detection NCO percentage composition is by chemical industry ministerial standard " isocyanate group content in HG/T2409-92 base polyurethane prepolymer for use as
Measurement " carry out.
3, detection solid content is carried out by national standard " measurement of GB/T 2793-1995 adhesive non-volatile content ".
Embodiment 1
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, by 140 grams of sulfonate dihydric alcohols (molecular weight 550, solid content 70%) and 110 grams of acetic acid second
Ester mixing, is stirring evenly and then adding into 300 grams of HDI trimers (solid content 100%), is warming up to 55~60 DEG C and reacts 2 hours, then
106.2 grams of HMDI are added, is warming up to 60 DEG C and reacts 1 hour, 70 DEG C are reacted 1 hour, and 80 DEG C are reacted 4 hours, and 90 DEG C are reacted 4 hours
The NCO percentage composition for surveying reactant afterwards stops reaction when NCO decline tends towards stability close to 14%；
B) blocked polyisocyanate prepolymer is prepared
50 DEG C are cooled to, 190g methyl ethyl ketoxime is added in four times, charge temperature is controlled at 50~55 DEG C, adds within 2 hours, add
It is reacted after complete material at 60~70 DEG C 1 hour, 75~80 DEG C are reacted 3 hours, are obtained blocked polyisocyanate prepolymer, that is, are closed
Type polyurethane curing agent；40 DEG C are cooled to, 282 grams of reaction products are taken out, gives over to the use of comparative test 1.
C) blocked polyurethane curing agent lotion is prepared
40 DEG C are cooled to, 120 grams of methylene chloride are added in remaining reaction mass, improves revolving speed extremely after mixing evenly
1500 revs/min, 413 grams of deionized waters are slowly added to, are added within about 10 minutes, are continued stirring and emulsifying 10 minutes；Vacuum pump is opened,
It 45 DEG C, vacuumizes 1 hour under 0.08MPa vacuum degree, then rise to 50 DEG C, is vacuumized under 0.08MPa vacuum degree 1 hour；Discharging,
Obtain blocked polyurethane curing agent lotion.
The appearance for being detected this example curing agent is the lotion of the micro- blue light of white, solid content 55%, viscosity 260mPas
(25 DEG C), solution be honored as a queen NCO% be 9.9%, pH value 7.Obtained blocked polyurethane curing agent lotion is placed at room temperature for 3 months
After observe, lotion is without lamination.
Comparative example 1
By 1 step b) of embodiment take out 282 grams of reaction products be added emulsifier in, agitator speed be adjusted to 2000 turns/
Point, 170 grams of deionized waters are slowly added to, are added within about 10 minutes, are continued stirring and emulsifying 10 minutes, discharging obtains blocked polyurethane
Curing agent white emulsion.
Obtained white emulsion is placed at room temperature, observation, lamination occurs in lotion after 24 hours.
Embodiment 2
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, 150 grams of sulfonate dihydric alcohols (molecular weight 550, solid content 70%) is mixed with 80 grams of acetone
It closes, is stirring evenly and then adding into 400 grams of TDI prepolymers (prepolymer of TDI and trimethylolpropane), is warming up to 55~60 DEG C of reactions
2 hours, 120 grams of MDI are added, react 1 hour at 60 DEG C, 70 DEG C are reacted 1 hour, and 80 DEG C are surveyed reactant after reaction 3 hours
NCO percentage composition stops reaction when NCO decline tends towards stability close to 11%；
B) blocked polyisocyanate prepolymer is prepared
50 DEG C are cooled to, 180g methyl ethyl ketoxime is added in four times, charge temperature is controlled at 50~55 DEG C, adds within 2 hours, add
It is reacted 1.5 hours after complete material at 65~70 DEG C, obtains blocked polyisocyanate prepolymer, i.e. blocked polyurethane curing agent；
40 DEG C are cooled to, 310 grams of reaction products are taken out, gives over to the use of comparative test 2.
C) blocked polyurethane curing agent lotion is prepared
40 DEG C are cooled to, 120 grams of methylene chloride are added in remaining reaction mass, improves revolving speed extremely after mixing evenly
1500 revs/min, 410 grams of deionized waters are slowly added to, are added within about 10 minutes, are continued stirring and emulsifying 10 minutes；Vacuum pump is opened,
It 45 DEG C, vacuumizes 2 hours under 0.08MPa vacuum degree；Discharging, obtains blocked polyurethane curing agent lotion.
The appearance for being detected this example curing agent is the lotion of the micro- blue light of white, solid content 50.2%, and viscosity is
300mPas (25 DEG C), solution be honored as a queen NCO% be 6.1%, pH value 7, the blocked polyurethane curing agent lotion room temperature that will be obtained
It is observed after placing 3 months, lotion is without lamination.
Comparative example 2
By 2 step b) of embodiment take out 310 grams of reaction products be added emulsifier in, agitator speed be adjusted to 2000 turns/
Point, 310 grams of deionized waters are slowly added to, are added within about 10 minutes, are continued stirring and emulsifying 10 minutes, discharging obtains blocked polyurethane
Curing agent white emulsion.
Obtained white emulsion is placed at room temperature, observation, lamination occurs in lotion after placing 2 hours, and it is small to place 4
When after lotion to become upper layer be water, lower layer is white bits.
Through the foregoing embodiment 1, the analysis of comparative example 1, embodiment 2, comparative example 2, it may be clearly seen that present invention envelope
The product usability of closed form urethane cures agent emulsion and blocked polyurethane curing agent solution prepared by CN107793544A
It can be different, usefulness of the present invention is so that properties of product are more stable, and purposes is more extensive, more preferable using craftsmanship.
Embodiment 3
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, by 120 grams of sulfonate dihydric alcohols (molecular weight 550, solid content 70%), 180 grams of tumers
Ester is mixed evenly, and 400 grams of MDI are added, and is heated to 50 DEG C and reacts 1 hour, rises to 70~75 DEG C and reacts 3 hours.It is cooled to
55 grams of trimethylolpropanes are added in 50 DEG C, 2 hours in four times, charging is both needed to for temperature in the kettle to be down to 50~55 DEG C every time, adds
After complete material 60~65 DEG C react 1 hour, 70~75 DEG C reaction 2 hours after survey reactant NCO percentage composition, when NCO decline
When tending towards stability close to 10%, stop reaction；
B) blocked polyisocyanate prepolymer is prepared
50 DEG C are cooled to, 92 grams of ethyl alcohol are added in four times, control charge temperature adds in 50~55 DEG C, 2 hours, continues
60~65 DEG C are maintained to react 2 hours.
C) blocked polyurethane curing agent lotion is prepared
40 DEG C are cooled to, 180 grams of methylene chloride are added, revolving speed is improved after mixing evenly to 1300 revs/min, is slowly added to
538 grams of deionized waters add for about 15 minutes, continue stirring and emulsifying 15 minutes；Open vacuum pump, at 45 DEG C, 0.08MPa vacuum degree
Under vacuumize 2 hours；Discharging, obtains blocked polyurethane curing agent lotion.
The appearance for being detected this example curing agent is the lotion of the micro- blue light of white, solid content 50%, viscosity 320mPas
(25 DEG C), solution be honored as a queen NCO% be 6.3%.
Embodiment 4
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, 104 grams of sulfonate dihydric alcohols (molecular weight 550, solid content 70%) is mixed with 200 grams of butanone
It closes, is stirring evenly and then adding into 400 grams of IPDI tripolymers, be warming up to 55~60 DEG C and react 1 hour, 60~70 DEG C are reacted 1 hour, then
80 grams of HMDI are added, 70 DEG C react 1 hour, 80 DEG C react 4 hours, 90 DEG C reaction 1 hour after survey reactant NCO percentage contain
Amount stops reaction when NCO decline tends towards stability close to 8.5%；
B) blocked polyisocyanate prepolymer is prepared
50 DEG C are cooled to, 140g methyl ethyl ketoxime is added in four times, charge temperature is controlled at 50~55 DEG C, adds within 2 hours, add
It is reacted after complete material at 60~70 DEG C 1 hour, 70~80 DEG C are reacted 3 hours；
C) blocked polyurethane curing agent lotion is prepared
40 DEG C are cooled to, 160 grams of dichloroethylene are added, revolving speed is improved after mixing evenly to 1200 revs/min, is slowly added to
432 grams of deionized waters add for about 10 minutes, continue stirring and emulsifying 10 minutes；Open vacuum pump, at 45 DEG C, 0.08MPa vacuum degree
Under vacuumize 1 hour, then rise to 50 DEG C, vacuumized under 0.085MPa vacuum degree 1 hour；It is solid to obtain blocked polyurethane for discharging
Agent lotion.
The appearance for being detected this example curing agent is the lotion of the micro- blue light of white, solid content 50.2%, and viscosity is
340mPas (25 DEG C), solution be honored as a queen NCO% be 7.0%.
Embodiment 5
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, 150 grams of sulfonate dihydric alcohols (molecular weight 550, solid content 70%) and 150 grams of acetic acid are different
Propyl ester mixing, is stirring evenly and then adding into 300 grams of PAPI, is warming up to 55~60 DEG C and reacts 2 hours, 70 DEG C are reacted 2 hours, and 80 DEG C anti-
The NCO percentage composition that reactant is surveyed after answering 1 hour stops reaction when NCO decline tends towards stability close to 14%；
B) blocked polyisocyanate prepolymer is prepared
50 DEG C are cooled to, 197g phenol is added in four times, charge temperature is controlled at 50~55 DEG C, adds within 2 hours, add material
It is reacted 2 hours at 70~75 DEG C afterwards；
C) blocked polyurethane curing agent lotion is prepared
40 DEG C are cooled to, 180 grams of dichloroethanes are added, revolving speed is improved after mixing evenly to 1000 revs/min, is slowly added to
330 grams of deionized waters add for about 10 minutes, continue stirring and emulsifying 10 minutes；Open vacuum pump, at 45 DEG C, 0.08MPa vacuum degree
Under vacuumize 1 hour, then rise to 50 DEG C, vacuumized under 0.085MPa vacuum degree 2 hours；It is solid to obtain blocked polyurethane for discharging
Agent lotion.
The appearance for being detected this example curing agent is micro- blue light white emulsion, solid content 55.1%, viscosity 280mPas
(25 DEG C), solution be honored as a queen NCO% be 10.5%.
Embodiment 6
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, by the dispersible sulfonated polyester dihydric alcohol of 160 grams of water (molecular weight 650, solid content 70%)
It is mixed with 120 grams of methyl isopropyl Ketones, is stirring evenly and then adding into 300 grams of HDI biurets (solid content 100%), is warming up to 55
~60 DEG C are reacted 1 hour, and 60~70 DEG C are reacted 3.5 hours, and 100 grams of IPDI are added, and are reacted at 70 DEG C 1 hour, 80 DEG C of reactions 3
Hour, 90 DEG C of NCO percentage compositions that reactant is surveyed after reaction 1 hour stop anti-when NCO decline tends towards stability close to 14%
It answers；
B) blocked polyisocyanate prepolymer is prepared
50 DEG C are cooled to, 276g epsilon-caprolactams are added in five times, charge temperature is controlled at 50~55 DEG C, adds within 2 hours,
It is reacted at 60~65 DEG C 1 hour after adding material, 70~75 DEG C are reacted 2 hours；
C) blocked polyurethane curing agent lotion is prepared
40 DEG C are cooled to, 220 grams of trichloro ethylenes are added, revolving speed is improved after mixing evenly to 1500 revs/min, is slowly added to
402 grams of deionized waters add for about 15 minutes, continue stirring and emulsifying 15 minutes；Open vacuum pump, at 45 DEG C, 0.08MPa vacuum degree
Under vacuumize 1 hour, then rise to 50 DEG C, vacuumized under 0.085MPa vacuum degree 2 hours；It is solid to obtain blocked polyurethane for discharging
Agent lotion.
The appearance for being detected this example curing agent is micro- blue light white emulsion, solid content 56.1%, viscosity 310mPas
(25 DEG C), solution be honored as a queen NCO% be 9.8%.
Embodiment 7
A) polyisocyanate prepolymers containing sulfonic acid group are prepared
In the reactor, 170 grams of sulfonate dihydric alcohols (molecular weight 600, solid content 70%) is mixed with 140 grams of acetone
It closes, is stirring evenly and then adding into 300 grams of HDI trimers, be warming up to 55~60 DEG C and react 1 hour, 60~70 DEG C are reacted 3 hours, then
104 grams of IPDI are added, 70 DEG C react 1 hour, 80 DEG C react 3 hours, 90 DEG C reaction 1 hour after survey reactant NCO percentage
Content stops reaction when NCO decline, which tends towards stability, connects 14%；
B) blocked polyisocyanate prepolymer is prepared
30 DEG C are cooled to, 230g3 is added in five times, 5- dimethyl pyrazole controls charge temperature at 30~40 DEG C, 2 hours
It adds, is reacted at 50~60 DEG C 1 hour after adding material, 60~75 DEG C are reacted 2 hours；
C) blocked polyurethane curing agent lotion is prepared
30 DEG C are cooled to, 210 grams of dichloroethylene are added, revolving speed is improved after mixing evenly to 1200 revs/min, is slowly added to
424 grams of deionized waters add for about 15 minutes, continue stirring and emulsifying 10 minutes；Open vacuum pump, at 45 DEG C, 0.08MPa vacuum degree
Under vacuumize 2 hours；Discharging, obtains blocked polyurethane curing agent lotion.
The appearance for being detected this example curing agent is micro- blue light white emulsion, solid content 55.4%, viscosity 450mPas
(25 DEG C), solution be honored as a queen NCO% be 9.5%.
Application examples 1
60 grams of blocked polyurethane curing agent lotion that embodiment 1 obtains directly stirs with 200 grams of polyaminoester emulsions and is mixed
Close, aqueous polyurethane baking vanish is made, by this baking finish construction template is made, 150 DEG C curing oven 60 minutes, be placed at room temperature for
After 24 hours, paint film property obtained is as follows: paint film appearance (range estimation) is flat and smooth；Gloss (60 °): >=92%；Hardness: shore
D58；Impact strength: 52KJ/m2；Adhesive force: 1 grade；Flexibility: 1mm；Water resistance (72h) is without exception.
The method of inspection: (60 °) of gloss are pressed GB/T 2571- by GB1730-79, impact strength by GB9754-2007, hardness
1995, adhesive force presses GB/T1733-1993 by GB1731-79 standard, water resistance by GB1720-89, flexibility.
Application examples 2
40 grams and 200 grams polyurethane dispersing liquids of the blocked polyurethane curing agent lotion of embodiment 2 are directly stirred, system
Aqueous polyurethane high-temp glue is obtained, room temperature is observed after storing 3 months, and mixed emulsion is without lamination.
It is compound with PET film that this aqueous polyurethane high-temp glue is used for PET film.Glue is applied to a piece of PET by coating machine
On film, it is placed in baking oven and toasts 2 minutes for 150 DEG C, take out, another PET film is compound on it, it is 80~90 through roller temperature
It is compound DEG C to roll hot pressing, after being placed at room temperature for 48 hours, by/T2791-1995 " adhesive T peel strength experimental method flexible material
To flexible material ", T-type peeling strength test is carried out, PET film is torn.
Application examples 3
60 grams and 200 grams water-compatible amino resins of the blocked polyurethane curing agent lotion of embodiment 3 are directly stirred, system
Aqueous amino-stoving varnish, template is made in its spraying application, 120 DEG C curing oven 30 minutes, after being placed at room temperature for 24 hours, system
The paint film property obtained is as follows: paint film appearance (range estimation) is flat and smooth；Gloss (60 °): >=86%；Hardness: shore D61；Impact is strong
Degree: 46KJ/m2；Adhesive force: 1 grade；Flexibility: 1mm；Water resistance (72h) is without exception.
Application examples 4
60 grams and 200 grams water-based acrylic resins of the blocked polyurethane curing agent lotion of embodiment 4 are directly stirred,
Be made Aqueous acrylic urethane's baking vanish, template is made in its spraying application, 160 DEG C curing oven 50 minutes, be placed at room temperature for
After 24 hours, paint film property obtained is as follows: paint film appearance (range estimation) is flat and smooth；Gloss (60 °): >=92%；Hardness: shore
D66；Impact strength: 62KJ/m2；Adhesive force: 1 grade；Flexibility: 1mm；Water resistance (72h) is without exception.
Application examples 5
40 grams and 200 grams polyaminoester emulsions of the blocked polyurethane curing agent lotion of embodiment 5 are directly stirred, and are made
Glue is applied on cloth cover, suede in plant by aqueous polyurethane high-temp glue by machine, then is put into 120 DEG C of baking oven and is solidified 30 minutes, room
After temperature is placed 24 hours, tests tensile strength, elongation at break, wearability, washing dimensional stability of flannelette etc. and meet suede
The strength character requirement of cloth, appearance, feel and comfort also comply with the requirement of flannelette.
Application examples 6
60 grams and 200 grams aqueous alkide resins of blocked polyurethane curing agent lotion that embodiment 6 obtains directly are stirred
Mixing, water alcohol acid polyurethane baking vanish is made, by this baking finish construction template is made, 120 DEG C curing oven 60 minutes, room
After temperature is placed 24 hours, paint film property obtained is as follows: paint film appearance (range estimation) is flat and smooth；Gloss (60 °): >=86%；Firmly
Degree: shore D42；Impact strength: 48KJ/m2；Adhesive force: 1 grade；Flexibility: 1mm；Water resistance (72h) is without exception.
The present invention is that the existence form of product is different from the main distinction of CN107793544A technical solution, and the present invention is
Exist with water emulsion, CN107793544A is to exist in the form of a solution.The difference of the two essentially consists in: the present invention is being made
Emulsion adjuvant is added after blocked polyurethane curing agent solution, then plus water and milk is melted into lotion.Reason for this is that this
After inventor has found that Waterborne Blocked Polyurethane curing agent solution adds water high speed to emulsify in practice, the lotion of formation must horse
It could store, if the lotion individually placed several hours formed, at most place one day, cream for a long time after above being mixed with water-base resin
Liquid can be layered, and generated polymer bits, cannot be mixed with again with water-base resin, cause the waste of raw material；And high speed emulsifies
When amount of water also have stringenter limitation, add water to lack emulsification bad, the formation polymer bits that added water more.In this way, user
When using watersoluble closed type polyurethane curing agent solution, on the one hand requires user to be equipped with high-speed emulsifying machine, on the other hand require
It could be emulsified when user's use and it is necessary to be mixed as early as possible with water-base resin.Since the resin types of user are various, purposes is respectively not
Identical, also different to the stoichiometric amount of curing agent, the factors such as product quantity on order is uncertain in addition cannot be configured in advance
The mixed emulsion of water-base resin and curing agent, can only be ready-to-use, i.e., when using water-based stoving paint or aqueous high-temp glue, could incite somebody to action
Waterborne Blocked Polyurethane curing agent solution adds water high speed to emulsify, and with how many with how many.Curing agent emulsion cannot be deposited individually
It puts, this brings the difficulty of many use aspects to user.Therefore, continue the blocked polyurethane solidification that research can be stored individually
Agent emulsion is the demand of market development.
The technical scheme is that emulsion adjuvant is added after watersoluble closed type polyurethane curing agent is made, add water
It is emulsified into product.Cream is also added in the case where having had hydrophilic sulfonic acid group in closed polyisocyanate molecule structure
The reason of changing auxiliary agent is: the present inventor analyzes watersoluble closed type polyurethane curing agent made of CN107793544A technical solution
The reason of adding water emulsification to be demulsified quickly later is that the particle of lotion is larger, and stability is poor.How just partial size can be made lesser
Emulsion particle becomes a technical issues that need to address.Only when adding water emulsification, by the oily polymer particle of water package
Smaller, even up to nanoscale, molecular level can just obtain the emulsion particle of partial size very little.Those skilled in the art generally consider to allow
Prepolymer is dissolved by a solvent completely, the active force between macromolecular be it is the smallest, so under high velocity agitation plus water emulsification energy
Form lesser emulsion particle.According to known to CN107793544A technical solution, manufactured watersoluble closed type polyurethane curing agent is place
Why not can that be emulsified into the lesser lotion of partial size in the state being completely dissolved by solvent? the present inventor further analyzes
CN107793544A technical solution, finds the solvent that prepolymer can be dissolved in watersoluble closed type polyurethane curing agent solution, together
When also be soluble in water, or be slightly soluble in water, when adding water emulsification, the solvent of script oleophylic swung to it is hydrophilic, i.e., to the dissolution of prepolymer
Property has dropped, and prepolymer is in incomplete dissolved state, polymer billet occurs, even if can not make to gather under high velocity agitation
The dispersion of object micelle is closed, so the partial size of lotion is bigger, stability is poor.Experiments have shown that: it is insoluble using prepolymer can be dissolved
Watersoluble closed type polyurethane is used as in the highly polar organic solvent (methylene chloride, dichloroethanes, dichloroethylene, trichloro ethylene) of water
The emulsion adjuvant of curing agent, manufactured curing agent emulsion is light blue white, and can store for a long time, will not be layered precipitation (related text
Offer report: for the partial size of lotion in 100~250nm, the color of lotion is Lan Baise, when emulsion particle diameter ﹥ 300nm, the face of lotion
Color is milky).Experiment also confirms, not soluble in water highly polar due to joined in polyisocyanate prepolymers after closure
Solvent when adding water emulsification, requires to substantially reduce, cream also may be implemented in 200 revs/min or more revolving speeds to the revolving speed of blender
Change.
Of the invention prepares blocked polyurethane curing agent lotion before adding water emulsification, and emulsion adjuvant is first added, and
Emulsion adjuvant is insoluble in the highly polar organic solvent of low boiling point of water, there is 3 features: 1. not soluble in water, 2. low boiling point, 3. by force
Polar organic solvent.When emulsion adjuvant is added in the reaction system, it is pre- that it highly polar makes it easier to dissolution polyisocyanates
Polymers, and dissolubility is very good, in being completely dissolved state；The immiscible property of it and water makes it have oleophylic phase and hydrophobic
Phase, even if it can also dissolve prepolymer well in water emulsification dispersion；Due to being emulsified auxiliary agent between prepolymer macromolecular
Small molecule is dispersed, and under high velocity agitation, prepolymer macromolecular is dispersed in water in the form of emulsion particle, and it is atomic small to form partial size
Lotion.The partial size of lotion is smaller, and emulsion intercalation method is better, and lotion obtained from this is highly stable, is unlikely to storing
It is layered or is demulsified in the process and be precipitated.After lotion is formed, prepolymer macromolecular is wrapped up by water phase, even if vacuum extraction is molten again
Agent will not make prepolymer macromolecular reunite, so emulsion intercalation method is very good, it can be individually long time stored.It is of the invention special
Different emulsion adjuvant plays the role of the generation of final lotion conclusive.
The low boiling dot characteristics of emulsion adjuvant of the invention are deviate from for the ease of the vacuum after formation lotion, certainly also optional
The not hydrophilic emulsion adjuvant of other similar oleophylics is selected, is in protection scope of the present invention.The preferred boiling point of the present invention 100 DEG C with
Under highly polar organic solvent be real VOC free environment-protecting polyurethane solidification in room temperature or 50 DEG C or less after vacuum removal
Agent emulsion.
Claims (10)
1. a kind of preparation method of blocked polyurethane curing agent lotion, it is characterised in that: the following steps are included:
A) polyisocyanate prepolymers containing sulfonic acid group are prepared: in organic solvent, with small molecule sulfonate dihydric alcohol, polyisocyanate
Cyanate prepolymer and diisocyanate are raw material, or are with small molecule sulfonate dihydric alcohol, diisocyanate and trihydroxylic alcohol
Raw material prepares the polyisocyanate prepolymers containing sulfonic acid group；
B) it prepares blocked polyisocyanate prepolymer: the polyisocyanate prepolymers containing sulfonic acid group is reacted with sealer,
Terminal isocyanate group is closed, blocked polyisocyanate prepolymer is obtained；
C) it prepares blocked polyurethane curing agent lotion: blocked polyisocyanate prepolymer is mixed with emulsion adjuvant, then plus
Water emulsification removes organic solvent, obtains blocked polyurethane curing agent lotion.
2. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1, it is characterised in that: step
A) polyisocyanate prepolymers of the preparation containing sulfonic acid group are any one of following methods:
Method one:
S1: small molecule sulfonate dihydric alcohol is dissolved in organic solvent, and polyisocyanate prepolymers are added and are reacted；
S2: diisocyanate is added and is reacted, the polyisocyanate prepolymers containing sulfonic acid group are obtained；
Method two:
S1: small molecule sulfonate dihydric alcohol is dissolved in organic solvent, and diisocyanate is added and is reacted；
S2: trihydroxylic alcohol is added and is reacted, the polyisocyanate prepolymers containing sulfonic acid group are obtained.
3. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1 or 2, it is characterised in that:
In step a), small molecule sulfonate dihydric alcohol molecular weight is 350~1000；Polyisocyanate prepolymers are diisocyanate and three
The prepolymer of first alcohol, TDI tripolymer, MDI tripolymer, HDI trimer, IPDI tripolymer, HDI biuret, in PAPI at least
It is a kind of；Diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI；Trihydroxylic alcohol is trimethylolpropane, three hydroxyls
At least one of methyl ethane, glycerol, 1,2,6- hexanetriol.
4. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1 or 2, it is characterised in that:
In step a), organic solvent is at least one of esters solvent, ketones solvent.
5. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1, it is characterised in that: step
B) in, sealer is hydrogen-containing compound, and the reactive hydrogen of hydrogen-containing compound and the molar ratio for the terminal isocyanate group being closed are
(1.02~1.2): 1.
6. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1 or 5, it is characterised in that:
In step b), the temperature of reaction is 20 DEG C~80 DEG C, and the time of reaction is 1h~5h.
7. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1, it is characterised in that: step
C) in, emulsion adjuvant is halogenated hydrocarbon solvent, and the additional amount of emulsion adjuvant is blocked polyisocyanate prepolymer solids gross mass
10%~50%.
8. a kind of preparation method of blocked polyurethane curing agent lotion according to claim 1 or claim 7, it is characterised in that:
In step c), adding the temperature of water emulsification is 20 DEG C~40 DEG C；The speed of agitator of emulsification is no less than 1000 revs/min；Emulsification when
Between be 5min~20min；The method for removing organic solvent is vacuum distillation.
9. a kind of blocked polyurethane curing agent lotion, it is characterised in that: be by preparation according to any one of claims 1 to 8
Method is made.
10. blocked polyurethane curing agent lotion as claimed in claim 9 is preparing aqueous polyurethane baking vanish and/or aqueous poly- ammonia
Application in ester high-temp glue.
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