CN107163207A - A kind of heat-resisting high solid content aqueous polyurethane emulsion and its preparation method and application - Google Patents
A kind of heat-resisting high solid content aqueous polyurethane emulsion and its preparation method and application Download PDFInfo
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- CN107163207A CN107163207A CN201710426761.7A CN201710426761A CN107163207A CN 107163207 A CN107163207 A CN 107163207A CN 201710426761 A CN201710426761 A CN 201710426761A CN 107163207 A CN107163207 A CN 107163207A
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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
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Abstract
The invention belongs to polyurethane material technical field, a kind of heat-resisting high solid content aqueous polyurethane emulsion and its preparation method and application is disclosed.The preparation method is：Polymer polyatomic alcohol and polyisocyanates are reacted the base polyurethane prepolymer for use as that end group is NCO bases is made, then small molecule chain extender and sulfonic group calixarenes hydrophilic chain extender are added under the conditions of organic solvent, reaction obtains polyurethane prepolymer solution, resulting solution is neutralized, remove organic solvent after emulsification, obtains the heat-resisting high solid content aqueous polyurethane emulsion.The present invention is using sulfonic group calixarene compound as hydrophilic chain extender, and gained aqueous polyurethane emulsion has more preferable heat resistance and Geng Gao solid content, can be applied to the fields such as coating, adhesive or ink.
Description
Technical field
The invention belongs to polyurethane material technical field, and in particular to a kind of heat-resisting high solid content aqueous polyurethane emulsion and
Its preparation method and application.
Background technology
Polyurethane is the high polymer material of a class function admirable, is widely used in coating, adhesive and ink etc. and becomes more meticulous
In product.With the development of science and technology with the continuous enhancing of mankind's environmental consciousness, various countries' environmental regulation is increasingly severe, traditional
The discharge capacity of volatile organic matter (VOC) is by more and more limitations in solvent borne polyurethane, therefore water-base polyurethane material
It is increasingly subject to pay attention to, using also more and more extensive.Now, in leather finish, fiber treatment and fabric coating, paper coating, painting
Many fields such as material, adhesive, ink, water-proof thermal insulation material, aqueous polyurethane, which shows, progressively substitutes solvent borne polyurethane
Trend.
Aqueous polyurethane is the new polyurethane system using water as decentralized medium.Because the evaporation latent heat of water is big, therefore often
The aqueous polyurethane seen is dried slower, it is difficult to the need for the fast pipeline production for adapting to modern industry.High solids content it is aqueous
Polyurethane is the effective means for improving its drying and forming-film speed.Improve the main side that solid content is water-based polyurethane adhesive research
One of to.The solid content of aqueous polyurethane product prepared by common synthetic technology is generally 20%~40%, so can not only be increased
Freight, and the drying time of aqueous polyurethane can be extended, be not suitable for its requirement for industrializing streamline construction.By several
The development of 10 years, makes some progress in the synthetic technology of high-solid content water-based polyurethane both at home and abroad.For example, patent CN
103360563 B, CN 105295817 A, CN 106118577 A etc. disclose some and prepare high-solid content water-based polyurethane
Technical method.
In addition, it is poor the heat resistance of typical aqueous polyurethane product (such as water-based polyurethane adhesive), 60
Long-term its performance when using will become deteriorations in DEG C environment, and heat resisting temperature gathers generally below 80 DEG C this severely limits aqueous
The popularization and application of urethane adhesive.For example, the Laminating adhesive of the thermophilic digestion packaging bag of packaged food is needed by high temperature resistant
Gluten substitute tests (120 DEG C, 40min)；Prepared in the wooden structures composite for building such as timber structure house, timber structure part
The middle polyurethane adhesive used needs still have excellent adhesive property when temperature is up to 90 DEG C；Automotive upholstery it is poly-
Urethane adhesive (temperature is up to 90 DEG C) in automobile exposure still will not soften；Sport footwear is in the hot environment of summer sweltering heat
Will not degumming, cracking during strenuous exercise.Therefore, improve heat resistance is for the practical application of the products such as water-based polyurethane adhesive
It is vital.
The linear block polymer that aqueous polyurethane is alternately made up of soft segment and hard section, its thermal decomposition performance is mainly by hard
Section influence, and amorphous regions in hard section region are probably more degradable part in hard section, therefore the chemical composition of hard section
And the structures shape heat endurance of polyurethane.Practice have shown that, improve the main method of water-based polyurethane adhesive heat resistance
Have following several：(1) inorganic component is introduced.Inorganic material is introduced by chemistry or physics method in aqueous polyurethane emulsion
Expect (such as SiO2Or TiO2Deng nano-particle, talcum powder, titanium dioxide, Ludox etc.) water-based polyurethane adhesive is prepared, it is to improve
The effective ways of its heat resistance.Patent CN105542111A is molten by adding silicon in the aqueous polyurethane dispersing liquid of synthesis
Glue, has been made a kind of transfer aluminum plated aqueous polyurethane emulsion of high temperature resistant.Patent CN104004486A is in aqueous polyurethane emulsion
Add the inorganic material such as silicone coupling agents, talcum powder, titanium dioxide and aerosil, be made it is heat-resist, at 120 DEG C
The aqueous adhesive not after-tacked.Patent CN 102153984B are with Nano-meter SiO_22For raw material, using the method for in-situ polymerization, it is made
Heat resistance preferable single-component water-based polyurethane adhesive.(2) additional curing agent.Patent CN103435760A,
CN104194706A, CN 106010189A are the methods by the external reinforcement agent in aqueous polyurethane emulsion, and double groups are made
Part water-based polyurethane adhesive, so as to improve the crosslink density after adhesive solidification, makes it have preferable resistance to elevated temperatures.
But, these double-component waterborne polyurethane products finally need to be compounded according to a certain percentage, its operation ease and adaptation
Property aspect be all further improved.(3) it is modified using other polymers.In the building-up process of aqueous polyurethane or aqueous
In polyurethane products, polyacrylate (patent CN 104531033A), melamine (patent CN104193916A), liquid are added
State polysulfide rubber (patent CN 104650787A), nitrile rubber (patent CN 105461891A) etc., can improve aqueous poly-
The heat resistance of urethane adhesive.(4) introducing cohesive energy is larger in the strand of aqueous polyurethane, degradation temperature is higher has
Machine rigid annular group.For example, patent CN104650319A is related to a kind of thermal polyurethane elastomer of structure containing rigid heterocyclic,
Patent CN103242504B is related to the aqueous thermal-resistant that a kind of polyalcohol containing heteroaromatic/flame-proof polyol reacts generation with isocyanates
Polyurethane resin.Research shows that the organic rigid cyclic group that induced one when base polyurethane prepolymer for use as is synthesized (mainly aromatic ring) can be bright
The aobvious melting temperature for improving polyurethane resin, so as to improve its temperature tolerance.In these compounds for containing rigid annular group,
The compound that one class contains calixarene structure gradually causes the concern of researcher.
Calixarenes be by the 2 of multiple phenol, 6 by methylene connect formed by the hollow macrocyclic oligoesters of a class, in
Early 20th century is found unintentionally and is determined by experiment during synthetic linear phenolic resin as cyclic tetramer：That is cup
[4] aromatic hydrocarbons.Then, researcher synthesizes cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons in succession again.By introducing sulphur in the contraposition of its phenolic hydroxyl group
Acid groups, can improve its water solubility, prepare water miscible calixarenes sulfonate.The structures shape of calixarenes sulfonate it not
Only there is higher fusing point, with good chemical stability and heat endurance, but also the characteristic with surfactant, energy
It is enough to be used for the synthesis of aqueous polyurethane as hydrophilic monomer.Therefore, theoretically calixarenes sulfonic acid can be completely used for
Prepare the aqueous polyurethane of excellent heat resistance.Have not yet to see the research report of this respect.
In a word, although at present both at home and abroad in the technology of preparing of high-solid content water-based polyurethane and heat resistance aqueous polyurethane
Make some progress, still, stability is good, building-up process favorable reproducibility high-solid content water-based polyurethane base preparing
On plinth, it is ensured that aqueous polyurethane has various excellent physical and mechanical properties, especially heat resistance in the application, in fact not
Easily, many work still do.Therefore, the aqueous poly- ammonia of heat-resist, solid content high (more than 50%) how is prepared
Ester product is still that one of subject matter for solving is needed in its application process.
The content of the invention
In place of the shortcoming and defect existed for above prior art, primary and foremost purpose of the invention is to provide a kind of heat-resisting
The preparation method of high solid content aqueous polyurethane emulsion.
Another object of the present invention is to provide a kind of heat-resisting high solid content water prepared by the above method to gather
Urethane emulsion.
It is still another object of the present invention to provide above-mentioned heat-resisting high solid content aqueous polyurethane emulsion coating, adhesive or
Application in the fields such as ink.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion, including following preparation process：
(1) preparation of performed polymer：By polymer polyatomic alcohol heating fusing after with polyisocyanates nitrogen protect and 75~
120~150min is reacted at 85 DEG C, the base polyurethane prepolymer for use as that end group is-NCO bases is made；
(2) dilution of performed polymer and chain extension：Performed polymer obtained by step (1) is cooled to 55~65 DEG C, added organic
Solvent reduces the viscosity of system, then addition small molecule chain extender and sulfonic group calixarenes hydrophilic chain extender, and reaction 60~
120min, obtains polyurethane prepolymer solution；
(3) neutralize, emulsify and desolvation：Prepolymer solution obtained by step (2) is cooled to 30 DEG C~40 DEG C, added molten
Solution has the deionized water of nertralizer, neutralized in the case where rotating speed is 5000~7000r/min high shear, emulsify 20~
40min, then removes organic solvent, obtains the heat-resisting high solid content aqueous polyurethane emulsion.
Preferably, the polymer polyatomic alcohol described in step (1) is included in PEPA and PPG at least
It is a kind of；The PEPA include molecular weight be 1000 or 2000 poly-epsilon-caprolactone glycol (PCL), molecular weight be 1000 or
2000 polyadipate BDO ester (PBA), the PCDL (PCDL) that molecular weight is 1000 or 2000, polyethers is more
First alcohol includes the polytetrahydrofuran diol (PTMG) that molecular weight is 1000 or 2000, the polypropylene glycol that molecular weight is 1000 or 2000
(PPG)；More preferably molecular weight be 2000 one kind or any two or more mixture as the present invention polymer polyol
Alcohol；The addition of polymer polyatomic alcohol accounts for 56.7%~63.2% of solids quality in final gained aqueous polyurethane emulsion.
Preferably, the polyisocyanates described in step (1) is that IPDI (IPDI), hexa-methylene two are different
At least one of cyanate (HDI), toluene di-isocyanate(TDI) (TDI)；More preferably IPDI (IPDI)；It is many
The addition of isocyanates accounts for 27.6%~32.4% of solids quality in final gained aqueous polyurethane emulsion.
Preferably, the organic solvent described in step (2) is at least one of acetone and butanone；More preferably butanone conduct
Organic solvent；The addition of organic solvent accounts for 165%~200% of solids quality in final gained aqueous polyurethane emulsion.
Preferably, the small molecule chain extender described in step (2) is ethylene glycol, diglycol, BDO
And at least one of hexylene glycol (BDO)；More preferably 1,4- butanediols (BDO) are small molecule chain extender；Small molecule chain extender
Addition accounts for 5.1%~7.1% of solids quality in final gained aqueous polyurethane emulsion.
Preferably, sulfonic group calixarenes hydrophilic chain extender described in step (2) includes p-sulfonic acid base cup [4] aromatic hydrocarbons
(C4AS), at least one of sulfonic group cup [6] aromatic hydrocarbons (C6AS) and sulfonic group cup [8] aromatic hydrocarbons (C8AS)；Preferred pair sulfonic group
Cup [4] aromatic hydrocarbons (C4AS) is hydrophilic chain extender；It is aqueous that the addition of sulfonic group calixarenes hydrophilic chain extender accounts for final gained
The 3.6%~5.2% of solids quality in polyaminoester emulsion.The structure such as following formula of p-sulfonic acid base cup [4] aromatic hydrocarbons (C4AS)
It is shown.
Preferably, the nertralizer described in step (3) is one kind in triethylamine, ammoniacal liquor, sodium hydroxide；More preferably
NaOH；The addition of nertralizer is added with the amount in 100% and in base polyurethane prepolymer for use as required for acidic-group.
Preferably, removed described in step (3) organic solvent refer to temperature be 50~70 DEG C, vacuum be 0.05~
Vacuum distillation removes organic solvent under conditions of 0.1MPa.
A kind of heat-resisting high solid content aqueous polyurethane emulsion, is prepared by the above method.Preferably, it is described aqueous poly-
The average grain diameter of urethane emulsion is 95~130nm, and solid content >=50wt%, viscosity is less than 500mPas.
Application of the above-mentioned heat-resisting high solid content aqueous polyurethane emulsion in the fields such as coating, adhesive or ink.
The principle of the present invention is the dihydromethyl propionic acid that carboxy-containing acid group is replaced using the calixarenes containing sulfonic acid group
(DMPA) as hydrophilic chain extender, the hydrophily of its sulfonate formed is better than carboxylate, with higher rate of ionization,
Which enhance the Zeta potential of latex particle " electric double layer " (zeta potential), stronger Coulomb repulsion can be formed between emulsion particle and is made
With prevention emulsion particle condenses, therefore is particularly suitable for preparing the aqueous polyurethane of high solids content.On the one hand, containing sulfonic acid group
The annular rigid group of calixarenes hydrophilic chain extender be introduced in the hard segment structure of aqueous polyurethane, this improves poly- ammonia
The heat decomposition temperature of ester.On the other hand, calixarenes contains multiple hydroxyl-OH ,-NCO that in theory can be with diisocyanate
Base reacts, and this polyhydroxy reaction actually increases the interior crosslink density of polyurethane, and the raising of crosslink density is also
Improve one of important channel of polymer heat-resistant.Therefore, the aqueous polyurethane emulsion prepared by the present invention has well resistance to
Hot property.Further, in order to prepare the aqueous polyurethane emulsion of high solids content, the present invention can be using the stronger butanone of dissolving power
Instead of the acetone used in standard aqueous polyurethane synthetic method, aqueous polyurethane, and this hair are synthesized using butanone method
Butanone consumption in bright is also greatly increased, it ensure that the polyurethane generated in course of reaction can well dissolve and form low
The solution of viscosity, so, a small amount of water need to be only added in emulsification can just be made that particle diameter is small, stably dispersing aqueous polyurethane
Emulsion.Butanone high volatility and water can form azeotropic mixture, therefore can be removed, reclaimed by vacuum distillation.So as to be prepared for one kind
The aqueous polyurethane emulsion that heat resistance is good, solid content is high.
The preparation method and resulting product of the present invention has the following advantages that and beneficial effect：
(1) present invention is using the not only sulphur containing annular rigid group but also containing hydrophilic sulfonic acid group and reactive hydroxyl
Acidic group calixarenes introduces annular rigid group as hydrophilic chain extender in the molecular structure of aqueous polyurethane, so that
Prepared polyurethane has good heat resistance；
(2) present invention replaces the dihydromethyl propionic acid (DMPA) of carboxy-containing acid group to make using the calixarenes containing sulfonic acid group
For hydrophilic chain extender, its sulfonate formed has higher rate of ionization, and which enhance latex particle " electric double layer "
Zeta potential (zeta potential), can form stronger electrostatic repulsion in latex intergranular, be conducive to the aqueous polyurethane of high solids content
Preparation；
(3) present invention further can replace being made in standard aqueous polyurethane synthetic method using the stronger butanone of dissolving power
Acetone, the butanone consumption synthesized using butanone method in aqueous polyurethane, and the present invention is also greatly increased, it ensure that
The polyurethane generated in course of reaction can dissolve and be formed the solution of low viscosity well, so, only need to add in emulsification
A small amount of water be just made average grain diameter for 95~130nm, viscosity be less than 500mPas, solid content >=50wt% have it is good
The aqueous polyurethane emulsion of good stability；
(4) present invention during aqueous polyurethane emulsion is prepared, can only using butanone this it is a kind of be easy to volatilization it is molten
Agent, is not used high boiling solvent, is less than 1% by butanone amount remaining in final products after vacuum distillation；
(5) present invention can further use the sulfonic acid group in non-volatile NaOH and in sulfonic group calixarenes, it is to avoid
In the preparation process of traditional carboxylic acid type aqueous polyurethane using aminated compounds such as in the neutralization polyurethane such as triethylamine
Carboxyl (DMPA) this step, thus completely eliminate the penetrating odor of volatile amine compound；
(6) aqueous polyurethane emulsion for preparing of the present invention, is with a wide range of applications, available for coating, adhesive and
In the fine chemicals such as ink, it is especially suitable for use as adhesive for shoemaking, thermophilic digestion packaging bag Laminating adhesive, builds wooden knot
Structure composite adhesive, automotive upholstery adhesive etc., it is possible to increase the heat resistance of these polyurethane adhesives
And service life.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) preparation of performed polymer：Molecular weight is added to equipped with agitator, thermometer and cold for 2000 PCL 80.0g
In the 500mL four-hole boiling flasks of solidifying pipe, then heating fusing adds 35.0gIPDI in logical nitrogen, is reacted at 80 DEG C
130min, is made the base polyurethane prepolymer for use as that end group is-NCO bases.
(2) dilution of performed polymer and chain extension：Performed polymer obtained by upper step reaction is cooled to 65 DEG C, adds 198.3g butanone drop
The viscosity of low system, then adds the mixed solution of 6.5g BDO and 15g butanone, adds the mixing of 5.1gC4AS and 15g butanone
Thing, continues to react 90min at 65 DEG C, polyurethane prepolymer solution is made.
(3) neutralize, emulsify and desolvation：Prepolymer solution obtained by the reaction of upper step is cooled to 35 DEG C, 123mL is added
1.10g NaOH deionized water is dissolved with, in the case where rotating speed is 7000r/min high shear, is neutralized, emulsified
35min.Finally, temperature be 60 DEG C, vacuum be vacuum distillation removing butanone under conditions of 0.1MPa, produce aqueous polyurethane
Emulsion.
Embodiment 2
(1) preparation of performed polymer：PBA 50.0g and the PPG 25.0g that molecular weight is 2000 are added to equipped with stirring
In the 500mL four-hole boiling flasks of device, thermometer and condenser pipe, then heating fusing adds IPDI 37.0g, 85 in logical nitrogen
120min is reacted at DEG C, the base polyurethane prepolymer for use as that end group is-NCO bases is made.
(2) dilution of performed polymer and chain extension：Performed polymer obtained by upper step reaction is cooled to 55 DEG C, adds 221.4g butanone drop
The viscosity of low system, then adds the mixed solution of 7.2g BDO and 15g butanone, adds the mixing of 6.6gC4AS and 15g butanone
Thing, continues to react 120min at 65 DEG C, polyurethane prepolymer solution is made.
(3) neutralize, emulsify and desolvation：Prepolymer solution obtained by the reaction of upper step is cooled to 30 DEG C, 121mL is added
1.42g NaOH deionized water is dissolved with, in the case where rotating speed is 6000r/min high shear, is neutralized, emulsified
40min.Finally, temperature be 50 DEG C, vacuum be vacuum distillation removing butanone under conditions of 0.05MPa, produce aqueous poly- ammonia
Ester emulsion.
Embodiment 3
(1) preparation of performed polymer：PCDL 42.0g and the PTMG 28.0g that molecular weight is 2000 are added to be equipped with and stirred
In the 500mL four-hole boiling flasks for mixing device, thermometer and condenser pipe, then heating fusing adds 40.0g IPDI in logical nitrogen,
150min is reacted at 75 DEG C, the base polyurethane prepolymer for use as that end group is-NCO bases is made.
(2) dilution of performed polymer and chain extension：Performed polymer obtained by upper step reaction is cooled to 60 DEG C, adds 173.5g butanone drop
The viscosity of low system, then adds the mixed solution of 8.8g BDO and 15g butanone, adds the mixing of 4.5gC4AS and 15g butanone
Thing, continues to react 60min at 65 DEG C, polyurethane prepolymer solution is made.
(3) neutralize, emulsify and desolvation：Prepolymer solution obtained by the reaction of upper step is cooled to 40 DEG C, 120mL is added
0.97g NaOH deionized water is dissolved with, in the case where rotating speed is 5000r/min high shear, is neutralized, emulsified
20min.Finally, temperature be 70 DEG C, vacuum be vacuum distillation removing butanone under conditions of 0.08MPa, produce aqueous poly- ammonia
Ester emulsion.
Embodiment 4
(1) preparation of performed polymer：PCL 38.0g and the PPG 34.0g that molecular weight is 2000 are added to equipped with stirring
In the 500mL four-hole boiling flasks of device, thermometer and condenser pipe, then heating fusing adds 39.0g IPDI, 78 in logical nitrogen
135min is reacted at DEG C, the base polyurethane prepolymer for use as that end group is-NCO bases is made.
(2) dilution of performed polymer and chain extension：Performed polymer obtained by upper step reaction is cooled to 65 DEG C, adds 188.8g butanone drop
The viscosity of low system, then adds the mixed solution of 8.2g BDO and 15g butanone, adds the mixing of 5.5gC4AS and 15g butanone
Thing, continues to react 100min at 65 DEG C, polyurethane prepolymer solution is made.
(3) neutralize, emulsify and desolvation：Prepolymer solution obtained by the reaction of upper step is cooled to 38 DEG C, 118mL is added
1.18g NaOH deionized water is dissolved with, in the case where rotating speed is 6000r/min high shear, is neutralized, emulsified
20min.Finally, temperature be 65 DEG C, vacuum be vacuum distillation removing butanone under conditions of 0.06MPa, produce aqueous poly- ammonia
Ester emulsion.
Comparative example
In addition to following three points are different, raw material types, consumption and synthesis technique and implementation involved by this comparative example
Example 1 is just the same：(1) p-sulfonic acid base cup [4] aromatic hydrocarbons in embodiment 1 is replaced using the dihydromethyl propionic acid (DMPA) of homogenous quantities
(C4AS)；(2) butanone in embodiment 1 is replaced using the acetone of homogenous quantities；(3), it is necessary to add ratio during underway and emulsification
The more water of embodiment 1 could obtain stable aqueous polyurethane emulsion, that is, the least quantity added is 182.5mL.Therefore, originally
The theoretical solid content of the last obtained aqueous polyurethane emulsion of comparative example is 40.8%.
Performance test is carried out to aqueous polyurethane emulsion obtained by above example and comparative example：
(1) test of emulsion average grain diameter, viscosity and solid content：
According to standard GB/T/T 11175-2002《Synthetic resin emulsion test method》Defined method is determined, and is determined
Average grain diameter, viscosity and the solid content of aqueous polyurethane emulsion, experimental result are as shown in table 1.
(2) thermal stability analysis
Aqueous polyurethane latex film is carried out using the type thermogravimetric analyzers of TGA 2050 of TA Instruments companies of the U.S.
Thermogravimetric analysis (TG) test.10mg or so sample is taken to be tested under nitrogen atmosphere, heating rate is 10 DEG C/min, temperature
Interval degree is 30 DEG C~600 DEG C.Experimental result is as shown in table 1.As seen from table, using p-sulfonic acid base cup [4] aromatic hydrocarbons as hydrophilic
Property chain extender can effectively improve the heat endurance of aqueous polyurethane latex film.
(3) heat resistance is tested
According to GB 19340-2014《Footwear and case and bag adhesive》And HG/T 2815-1996《Adhesive for shoes heat resistance
Test method creep method》, it is 100 DEG C, in the case that counterweight weight is 1.5kg in experimental temperature, determines and pass through aqueous polyurethane
The time of experience is completely exfoliated in two PET test pieces that emulsion is bonded together, and experimental result is as shown in table 1.As seen from table,
It is completely exfoliated and is passed through by two PET test pieces measured by binding agent using the aqueous polyurethane emulsion of the embodiment of the present invention 1~4
The time gone through is all higher than 720min, and uses the aqueous polyurethane emulsion in comparative example to be shelled completely for the test piece obtained by binding agent
From the time then much shorter of experience.This shows that the heat resistance of the aqueous polyurethane obtained by embodiment 1~4 is more preferable.Therefore, use
P-sulfonic acid base cup [4] aromatic hydrocarbons can effectively improve the heat resistance of aqueous polyurethane as hydrophilic chain extender.
The Property of Waterborne Polyurethane test result of table 1
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion, it is characterised in that including following preparation process：
(1) preparation of performed polymer：It will be protected and 75~85 DEG C in nitrogen with polyisocyanates after polymer polyatomic alcohol heating fusing
120~150min of lower reaction, is made the base polyurethane prepolymer for use as that end group is-NCO bases；
(2) dilution of performed polymer and chain extension：Performed polymer obtained by step (1) is cooled to 55~65 DEG C, organic solvent is added
The viscosity of reduction system, then adds small molecule chain extender and sulfonic group calixarenes hydrophilic chain extender, reacts 60~120min,
Obtain polyurethane prepolymer solution；
(3) neutralize, emulsify and desolvation：Prepolymer solution obtained by step (2) is cooled to 30 DEG C~40 DEG C, addition is dissolved with
The deionized water of nertralizer, is neutralized in the case where rotating speed is 5000~7000r/min high shear, emulsifies 20~40min,
Then organic solvent is removed, the heat-resisting high solid content aqueous polyurethane emulsion is obtained.
2. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 1, it is characterised in that：
Polymer polyatomic alcohol described in step (1) includes at least one of PEPA and PPG；The polyester is more
It is 1000 or 2000 poly-epsilon-caprolactone glycol, polyadipate 1,4- butanediol esters, PCDL that first alcohol, which includes molecular weight,；
The PPG includes polytetrahydrofuran diol, polypropylene glycol of the molecular weight for 1000 or 2000；Polymer polyatomic alcohol
Addition accounts for 56.7%~63.2% of solids quality in final gained aqueous polyurethane emulsion.
3. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 1, it is characterised in that：
Polyisocyanates described in step (1) is IPDI, hexamethylene diisocyanate, toluene di-isocyanate(TDI)
At least one of；The addition of polyisocyanates account for solids quality in final gained aqueous polyurethane emulsion 27.6%~
32.4%.
4. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 1, it is characterised in that：
Organic solvent described in step (2) is at least one of acetone and butanone；The addition of organic solvent accounts for final gained water
The 165%~200% of solids quality in property polyaminoester emulsion.
5. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 4, it is characterised in that：
Described organic solvent is butanone.
6. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 1, it is characterised in that：
Small molecule chain extender described in step (2) is at least one in ethylene glycol, diglycol, 1,4- butanediols and hexylene glycol
Kind；The addition of small molecule chain extender accounts for 5.1%~7.1% of solids quality in final gained aqueous polyurethane emulsion.
7. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 1, it is characterised in that：
Sulfonic group calixarenes hydrophilic chain extender described in step (2) include p-sulfonic acid base cup [4] aromatic hydrocarbons, sulfonic group cup [6] aromatic hydrocarbons and
At least one of sulfonic group cup [8] aromatic hydrocarbons；It is aqueous poly- that the addition of sulfonic group calixarenes hydrophilic chain extender accounts for final gained
The 3.6%~5.2% of solids quality in urethane emulsion.
8. a kind of preparation method of heat-resisting high solid content aqueous polyurethane emulsion according to claim 1, it is characterised in that：
Nertralizer described in step (3) is one kind in triethylamine, ammoniacal liquor, sodium hydroxide；The addition of nertralizer is neutralized with 100%
Amount addition in base polyurethane prepolymer for use as required for acidic-group.
9. a kind of heat-resisting high solid content aqueous polyurethane emulsion, it is characterised in that：By described in any one of claim 1~8
Method is prepared；The average grain diameter of the aqueous polyurethane emulsion is 95~130nm, and solid content >=50wt%, viscosity is less than
500mPa·s。
10. a kind of heat-resisting high solid content aqueous polyurethane emulsion described in claim 9 is in coating, adhesive or ink area
Application.
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| CN111410730A (en) * | 2020-04-28 | 2020-07-14 | 厦门威亮光学涂层技术有限公司 | Polyurethane emulsion and anti-reflection coating liquid prepared from same |
| CN111410730B (en) * | 2020-04-28 | 2022-03-29 | 厦门威亮光学涂层技术有限公司 | Polyurethane emulsion and anti-reflection coating liquid prepared from same |
| CN112175567A (en) * | 2020-10-29 | 2021-01-05 | 烟台德邦科技有限公司 | Hydrolysis-resistant anti-settling conductive adhesive and preparation method thereof |
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