CN107446105A - A kind of sulfonic waterborne polyurethane emulsion, its product and preparation method thereof - Google Patents
A kind of sulfonic waterborne polyurethane emulsion, its product and preparation method thereof Download PDFInfo
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- CN107446105A CN107446105A CN201710622512.5A CN201710622512A CN107446105A CN 107446105 A CN107446105 A CN 107446105A CN 201710622512 A CN201710622512 A CN 201710622512A CN 107446105 A CN107446105 A CN 107446105A
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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Abstract
The invention discloses a kind of sulfonic waterborne polyurethane emulsion, its product and preparation method thereof, it is characterized in that, include polyisocyanates, polyvalent alcohol, sulfonate functional polyether Glycols type hydrophilic chain extender and solvent, the advantages of sulfonic waterborne polyurethane emulsion of the present invention, is, it can largely reduce the dosage of organic solvent, carboxylic acid and nertralizer, and preparation method is simple and environmentally friendly；Sulfonic waterborne polyurethane emulsion of the present invention also has good stability, therefore, has more preferably hydrolytic resistance and yellowing resistance by its obtained glued membrane.
Description
Technical field
The present invention relates to a kind of sulfonic waterborne polyurethane emulsion, its product and preparation method thereof, belong to polymeric material
Technical field.
Background technology
Polyurethane is widely used in the fields such as coating, adhesive, ink, leather processing, weaving, and performance is excellent, mesh
It is preceding industrially still largely to use organic solvent type polyurethane, to reduce system viscosity or dissolving reactant, commonly use organic solvent master
To include acetone, DMF and/or 1-METHYLPYRROLIDONE etc., acetone is prepared in aqueous polyurethane emulsion to be terminated
Partly or entirely removed through the mode being evaporated under reduced pressure afterwards, and DMF and 1-METHYLPYRROLIDONE are due to boiling point
It is of a relatively high, then it is typically remaining in emulsion.Therefore aqueous polyurethane emulsion industrially prepared at present is not all truly
Organic solvent-free participate in emulsion system, that is, a certain degree of volatility during preparation and use be present in it
The release of organic compound (VOC), and cause to form the health of workmen and consumer serious threat, national governments are also
Make laws and limited the content of VOC or hazardous air pollutants (HAP) in polyurethane product.
Aqueous polyurethane emulsion is using water as decentralized medium, has that nontoxic, not have flammable, environment-friendly and cost low
The advantages that, it has also become the important research direction of current polyurethane field.Aqueous polyurethane emulsion retains conventional organic solvents type and gathered
The features such as high gloss of urethane, high intensity, high-wearing feature, high resiliency, high gluing, lower temperature resistance and fatigue durability, and have
The advantage such as have transportation safety, good operational environment, viscosity unrelated with polymer molecular weight, at the same avoid organic solvent type polyurethane because
Problem of environmental pollution caused by a large amount of volatile organic solvents of generation in use.
Traditional waterborne polyurethane emulsion is expanded by oligomer dihydric alcohol, diisocyanate, hydrophilic chain extender and small molecule
The compositions such as chain agent, it is made through disperseing in addition polymerization and water, and compared with organic solvent type polyaminoester emulsion, except being used
Decentralized medium it is different outer, the synthesis key of aqueous polyurethane emulsion is to use hydrophilic chain extender, the hydrophilic chain extender
Hydrophilic radical can be introduced in polyurethane molecular structure, so that aqueous polyurethane emulsion has good dispersiveness or self-emulsifying
Energy.For example, the i.e. open one kind of the A of the prior art US 5470907 and A of US 6017998 is with dihydromethyl propionic acid (DMPA)
For the preparation method of the aqueous polyurethane emulsion of hydrophilic chain extender；The A of CN 101475678 separately disclose one kind with ethylenediamine base second sulphur
Sour sodium (AAS) is the preparation method of the aqueous polyurethane emulsion of main hydrophilic chain extender；The A of US 4870129 disclose one kind with two
Hydroxymethyl propionic acid and the preparation method that ethylenediamine base ethyl sulfonic acid sodium is the aqueous polyurethane emulsion of hydrophilic chain extender altogether；US 2006/
0036054 A1 discloses a kind of preparation method of sulfonate-functional polyester polyols, can be with the soft segment of polyurethane.
At present the anionic hydrophilic chain extender involved by aqueous polyurethane emulsion be broadly divided into carboxylic acid type chain extender and
Two kinds of sulfonate type chain extender, compared to carboxylic acid type chain extender (e.g., DMPA/DMBA), sulfonate type chain extender has more preferably
Hydrophily, therefore in the suitable polyurethane of preparation hydrophilicity, compared to carboxylic acid type chain extender, sulfonate type chain extender institute
The mole dosage related to is less, and because the ion in polyurethane chain is reduced, electrostatic repulsion weakens, therefore hydration volume will not be rapid
Increase causes system viscosity to rise, therefore sulfonate type chain extender is more beneficial for preparing the aqueous polyurethane emulsion of high solids content.
In addition, it need to additionally provide neutralization before water emulsification step is added using carboxylic acid type chain extender (e.g., DMPA/DMBA)
Salt-forming steps.Now widely used nertralizer is triethylamine, so, is neutralized using triethylamine into after salt, then be made through emulsification
Aqueous polyurethane emulsion in, it would still be possible to remain triethylamine, cause the aqueous polyurethane emulsion have unpleasant penetrating odor it
Shortcoming, and triethylamine also may decompose and volatilize during emulsion storage, so as to reduce the steady of aqueous polyurethane emulsion
It is qualitative.Compared to this, because sulfonate type chain extender is neutrality, thus do not need then during emulsion dispersion in another addition and
Agent, it can effectively avoid foregoing there is the problem of unpleasant penetrating odor or decomposition, volatilization；Furthermore because sulfonate type chain extender has
There is good storage stability and do not influenceed by external environment condition (e.g., temperature), therefore in obtained aqueous polyurethane emulsion physical property
Deviation is smaller, and aqueous polyurethane emulsion product has higher repeatability and stability, effective monitoring quality and can be advantageous to big
Amount production.
But sulfonate type chain extender in the prior art, still need to make acetone regulating system viscosity in dispersion process, so
And in order to meet the requirement of current environmental protective polymer material, therefore after sulfonic acid type water-based polyurethane product is made, need extra
Through being evaporated under reduced pressure step to remove acetone.But processing procedure involved by foregoing acetone is cumbersome, time-consuming and increase manufacturing cost, and
Through being evaporated under reduced pressure removed acetone, the anxiety for still having VOC emission, in other words, in fact existing manufacture aqueous polyurethane emulsion
Processing procedure be not loopful protect processing procedure.
The content of the invention
It is an object of the invention to provide a kind of environmentally friendly sulfonic waterborne polyurethane emulsion, its product and its manufacture method；
It is water-based poly- further to provide the sulfonic acid type for being not required to add any organic solvent, carboxylic acid and/or nertralizer in a kind of preparation process
Urethane emulsion, its product and its manufacture method, preparation method provided by the invention is simple and environmentally friendly, and obtained emulsion is also
With good stability, obtained glued membrane has more excellent hydrolytic resistance and yellowing resistance.Sulfonic acid type provided by the invention
Aqueous polyurethane emulsion and preparation method thereof is not only the purpose for reaching environmental protection from manufacture end, and sulfonic acid type provided by the invention is water-based
Polyaminoester emulsion can also be widely used in the products such as coating or solid.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of sulfonic waterborne polyurethane emulsion, include polyisocyanates, polyvalent alcohol, sulfonate functional polyether Glycols
Type hydrophilic chain extender and solvent.
Each component is described in detail below.
1st, polyisocyanates
Sulfonic waterborne polyurethane emulsion of the present invention, for polyisocyanates and have no special requirements.The present invention is suitable
Polyisocyanates more preferably includes diisocyanate, and the diisocyanate includes one kind or several in consisting of
Kind：Toluene di-isocyanate(TDI) (TDI), 1,4- tetramethylene diisocyanates, 1,6- hexamethylene diisocyanates (HDI), 1,
The dimethylene diisocyanates of 12- ten, hexamethylene -1,3- diisocyanate, hexamethylene -1,4- diisocyanate, isophorone
Diisocyanate (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate (HMDI),
Hexamethylene diisocyanate (HDI), polymethylene multi-phenenyl isocyanate (PAPI), XDI (XDI),
Naphthalene -1,5- diisocyanate (NDI), Methylcyclohexyl diisocyanate (HTDI), tetramethylxylylene diisocyanate
And its mixture (TMXDI).More preferably polyisocyanates is IPDI (IPDI), toluene diisocynate
Ester (TDI), 1,6- hexamethylene diisocyanates (HDI), double-hexyl methane diisocyanate (HMDI), diphenyl methane 4,
4- diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI).
An embodiment in the present invention, the total solid content based on the sulfonic waterborne polyurethane emulsion calculate, with
Percentage by weight represents that the content of the polyisocyanates is 5~35%, such as：6%th, 8%, 10%, 12%, 14%, 16%,
18%th, 20%, 22%, 24%, 26%, 28%, 30%, 32% or 34%, be more preferably 10 to 30%, more preferably 15 to
25%.
2nd, polyvalent alcohol
Sulfonic waterborne polyurethane emulsion of the present invention, for polyvalent alcohol and have no special requirements.The present invention is applicable
Polyvalent alcohol include following polyvalent alcohol composition in one or more：PEPA, poly-lactone polyol, polyether polyols
Alcohol, polycarbonate polyol, polythiaether polyol, mixed the polymers polyalcohol and its mixture of polyethers and polyester.The polyvalent alcohol compared with
Preferably include polyethylene glycol, polyoxypropyleneglycol, poly- tetrahydrofuran ether glycol, poly butylene succinate, polyadipate oneself
Diol ester, poly adipate succinic acid ester, polyadipate ethylene glycol butanediol ester or poly (propylene carbonate) dihydric alcohol, can be according to difference
Finished product characteristic selects.
An embodiment in the present invention, the polyvalent alcohol molecular weight are 600 to 5,000, such as：800、1000、
1200、1400、1600、1800、2000、2200、2400、2600、2800、3000、3200、3400、3600、3800、4000、
4200th, 4400,4600 or 4800, it is more preferably 1,000 to 4,000.
An embodiment in the present invention, the total solid content based on the sulfonic waterborne polyurethane emulsion calculate, with
Percentage by weight represents that the content of the polyvalent alcohol is 45~80%, such as：46%th, 48%, 50%, 52%, 54%, 56%,
58%th, 60%, 62%, 64%, 66%, 68%, 70%, 72% or 74%, be more preferably 50 to 75%, more preferably 55 to
70%.
3rd, sulfonate functional polyether Glycols type hydrophilic chain extender
The hydrophilic chain extension of sulfonate functional polyether Glycols type contained by sulfonic waterborne polyurethane emulsion of the present invention
Agent has the structure such as Formulas I：
Wherein R1For the three-level alkyl with 2 to 14 C atoms, such as there is the alkyl of 2 to 14 C atoms, more preferably for
Three-level straight-chain alkyl with 2 to 14 C atoms, such as there is the straight chained alkyl of 2 to 14 C atoms, more preferably with 2 to 6
The three-level straight-chain alkyl of individual C atoms, such as there is the straight chained alkyl of 2 to 6 C atoms；M+It is the metal ion of positively charged, more preferably
For alkali metal ion, more preferably sodium or potassium ion；And R2To R5Hydrogen or the alkyl with 1 to 6 C atom are each independently,
More preferably it is to be each independently hydrogen or the straight chained alkyl with 1 to 6 C atom, more preferably R2And R3Each independently of one another
For propyl group or butyl and R4And R5For methyl or ethyl.
According in the present invention one, more preferably embodiment, the sulfonate functional polyether Glycols type hydrophilic chain extender have
Double -1,4- (2- hydroxy propyloxy groups) -2- propylbutyl ethers sulfonate structures (Bis-1,4- (2- as shown in Formula II
hydroxypropoxy)-2propoxybutane sulfonate)。
Wherein M+It is the metal ion of positively charged, is more preferably alkali metal ion, more preferably sodium or potassium ion.According to this
A preferred embodiment in invention, the sulfonate functional polyether Glycols type hydrophilic chain extender include one in consisting of
Kind is several：Double -1,4- (2- hydroxy propyloxy groups) -2- propylbutyl ethers sodium sulfonate (sodium bis-1,4- (2-
Hydroxypropoxy) -2propoxybutane sulfonate), double -1,4- (2- hydroxyl-oxethyls) -2- ethoxy butanes
Potassium sulfonate and double -1,4- (2- hydroxyl-oxethyls) -2- ethoxy butane sodium sulfonates.
According to one embodiment of the invention, the total solid content meter based on the sulfonic waterborne polyurethane emulsion, with weight
Percentage represents that the content of the sulfonate functional polyether Glycols type hydrophilic chain extender is 1 to 35%, such as：2%th, 4%,
6%th, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32% or 34%, compared with
Preferably 5 to 25%, more preferably 10 to 20%.
The sulfonate functional polyether Glycols type hydrophilic chain extender that the invention described above defines, its advantage are：
Compared to conventional amidosulfonic acid salt form hydrophilic chain extender, the sulfonate functional polyether Glycols type hydrophilic chain extender is reacting
During, the reaction of its hydroxyl and polyisocyanates is more gentle, therefore will not increase the viscosity of formed prepolymer suddenly,
Control reaction can be easier to carry out, and substantial amounts of acetone need not be added to reduce system viscosity under preferable situation.
On the other hand, compared to other sulfonate functional polyether Glycols type hydrophilic chain extenders, the sulphur defined above
Hydrochlorate functional polyethers binary alcohol type hydrophilic chain extender has lower molecular weight, therefore a small amount of addition can introduce sulfonic acid group,
To reduce manufacturing cost；In addition, the process of sulfonic waterborne polyurethane emulsion is being prepared, from sulfonate official as defined above
Energy polyether Glycols type hydrophilic chain extender, then can avoid using substantial amounts of organic solvent, and be not required to carry out extra neutralization into salt
Step, the removal step program of complexity is omitted, and simplify synthesis technique.
4th, catalyst
Sulfonic waterborne polyurethane emulsion of the present invention can comprise additionally in catalyst as needed.Suitable for the present invention
The catalyst of the sulfonic waterborne polyurethane emulsion includes the one or more in consisting of：Tertiary amine catalyst, organotin
Catalyst or non-tin metal compound catalyst.More preferably include stannous octoate or dibutyl tin laurate.
According to one embodiment of the invention, the total solid content meter based on the sulfonic waterborne polyurethane emulsion, with weight
Ppm represents that the content of the catalyst is 0 to 200ppm, such as：10ppm、20ppm、30ppm、40ppm、50ppm、60ppm、
70ppm、80ppm、90ppm、100ppm、110ppm、120ppm、130ppm、140ppm、150ppm、160ppm、170ppm、
180ppm or 190ppm, it is more preferably 0 to 150ppm, more preferably 0 to 100ppm.
5th, small molecule chain extender
Sulfonic waterborne polyurethane emulsion of the present invention can comprise additionally in small molecule chain extender as needed.According to this
One embodiment of invention, the small molecule chain extender include the one or more in following small molecule chain extender composition：Ethylenediamine,
Hexamethylene diamine, phenylenediamine, diethanol amine, polyoxypropylene triamine, diethylenetriamine, IPD, m-xylene diamine or methyl
Diethanol amine.
According to one embodiment of the invention, the total solid content meter based on the sulfonic waterborne polyurethane emulsion, with weight
Percentage represents that the content of the small molecule chain extender is 0.1 to 20%, such as：0.2%th, 0.3%, 0.4%, 0.5%,
0.6%th, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%,
13%th, 14%, 15%, 16%, 17%, 18% or 19%, it is more preferably 0.5 to 15%, more preferably 1 to 10%.
6th, other hydrophilic chain extenders
Sulfonic waterborne polyurethane emulsion of the present invention also includes the non-hydrophilic expansion of sulfonate functional polyether Glycols type
Other hydrophilic chain extenders of chain agent.According to one embodiment of the invention, other described hydrophilic chain extenders include following hydrophilic
Property chain extender composition in one or more：Dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxy half ester, second diaminourea second sulphur
Sour sodium, diamino benzene sulfonic acid sodium, diaminopropionic acid or diaminobutyric acid.
According to one embodiment of the invention, the total solid content meter based on the sulfonic waterborne polyurethane emulsion, with weight
Percentage represents that the content of other hydrophilic chain extenders is 0.1 to 20%, such as：0.2%th, 0.3%, 0.4%, 0.5%,
0.6%th, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%,
13%th, 14%, 15%, 16%, 17%, 18% or 19%, it is more preferably 0.5 to 15%, more preferably 1 to 10%.
7th, crosslinking agent
Sulfonic waterborne polyurethane emulsion of the present invention can comprise additionally in crosslinking agent as needed, close with lifting crosslinking
Degree, increase the hydrolytic resistance of aqueous polyurethane emulsion.According to one embodiment of the invention, the crosslinking agent includes following crosslinking agent
One or more in composition：Aliphatic isocyanates in order, polyaziridine, water-base epoxy based cross-linker, carbon Asia acid amides crosslinking agent or
Melamine formaldehyde resin (U.S. resistance to ware).The carbon Asia acid amides crosslinking agent is more preferably GSI type carbon Asia acid amides.
According to one embodiment of the invention, based on the total of the sulfonic waterborne polyurethane emulsion, with percentage by weight
Represent, the content of crosslinking agent is 0 to 20%, such as：1%th, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%,
11%th, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%, be more preferably 2 to 15%, more preferably 5 to
10%.
8th, solvent
Include water suitable for the solvent of sulfonic waterborne polyurethane emulsion of the present invention, more preferably solvent substantially by
Water is formed.
According to one embodiment of the invention, based on the gross weight meter of the sulfonic waterborne polyurethane emulsion, with weight hundred
Divide than representing, the solvent is 55 to 80%, such as：56%th, 58%, 60%, 62%, 64%, 66%, 68%, 70%,
72%th, 74%, 76% or 78%, it is more preferably 60 to 75%, it is further preferred that being 65 to 70%.
According to the more preferably embodiment of the present invention, based on the gross weight meter of the sulfonic waterborne polyurethane emulsion,
In terms of weight percentage, the content of organic solvent contained in the solvent is 5.0% or less, such as：4.5% or less,
4.0% or less, 3.5% or less, 3.0% or less, 2.5% or less, 2.0% or less, 1.5% or less, 1.0%
Or it is less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or more
Less, 0.3% or less, 0.2% or less or 0.1% or less, it is more preferably 1.0% or less, is more preferably entirely free of
Any organic solvent.
According to the more preferably embodiment of the present invention, based on the gross weight meter of the sulfonic waterborne polyurethane emulsion,
In terms of weight percentage, acetone contained in the solvent, DMF and/or 1-METHYLPYRROLIDONE contain
Measure as 5.0% or less, such as：4.5% or less, 4.0% or less, 3.5% or less, 3.0% or less, 2.5% or more
Less, 2.0% or less, 1.5% or less, 1.0% or less, 0.9% or less, 0.8% or less, 0.7% or less,
0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less or 0.1% or less, compared with
Preferably 1.0% or less, more preferably it is entirely free of any acetone, DMF and/or N- crassitudes
Ketone.
Therefore, sulfonic waterborne polyurethane emulsion of the present invention has the advantages that：
A) aqueous polyurethane emulsion of the present invention can omit conventional carboxylic acid salt component institute using sulfonate as hydrophilic radical
The neutralization reaction related additionally to, and because the polyurethane prepolymer formed in emulsion includes sulfonate hydrophilic radical, it is described poly-
Urethane prepolymer has hydrophily, therefore can be directly dissolved in water, and it is glutinous to be not required to additionally to add acetone drop, therefore the sulfonic acid type of the present invention
Aqueous polyurethane emulsion more meets environmental requirement.Further, since the polyurethane prepolymer that aqueous polyurethane emulsion of the present invention is formed
Thing is water-soluble, therefore when using only water as solvent, improves stir speed (S.S.) using existing machine of mixing, be not necessary to separately use homogeneous
Machine, you can sulfonic waterborne polyurethane emulsion is successfully made.
B) the straight chain type sulfonate functional polyether Glycols type parent that sulfonic waterborne polyurethane emulsion of the present invention preferably uses
Water chain extender, the flexibility of formed glued membrane can be increased.
C) sulfonic waterborne polyurethane emulsion of the present invention additionally comprises crosslinking agent according to demand, can be lifted originally be inclined to it is water-soluble
Property polyurethane crosslink density, increase hydrolytic resistance.
D) sulfonic waterborne polyurethane emulsion of the present invention is particularly suitable for use in the products such as coating and solid, its functional and
It is with a wide range of applications.
The present invention also provides a kind of glued membrane, for the ink resin of soft material, coating, bed material, then PUR, use tree
Fat, the glued membrane are as obtained by sulfonic waterborne polyurethane emulsion as described above.
The present invention also provides a kind of method for preparing sulfonic waterborne polyurethane emulsion, and it comprises the following steps：
1. mix polyvalent alcohol and sulfonate functional polyether Glycols type hydrophilic chain extender；
2. polyisocyanates is added in the mixture, so that polyurethane prepolymer is made；And
3. solvent is added in the polyurethane prepolymer, it is water-based poly- so that sulfonic acid type is made to emulsify the polyurethane prepolymer
Urethane emulsion.
According to one embodiment of the invention, blend step more preferably temperature is 50 DEG C or higher in above-mentioned steps 1, more preferably
To be carried out at 60 DEG C or higher of temperature.
According to one embodiment of the invention, in above-mentioned steps 2 more preferably temperature be 50 DEG C or higher, more preferably 65 to
Carried out at a temperature of 95 DEG C, and the reaction time is in 1 to 7 hour, in preferably 2 to 5 hours, you can obtain polyurethane prepolymer produce
Thing.
According to one embodiment of the invention, catalyst as described above can add in step 2.
According to one embodiment of the invention, in above-mentioned steps 3 in emulsifying step, selected solvent includes water, more preferably
The solvent be substantially be made up of water.
According to one embodiment of the invention, small molecule chain extender as described above, such as ethylenediamine can be in steps 3
Added after emulsifying step.
It is involved in the preparation method of sulfonic waterborne polyurethane emulsion of the present invention according to the more preferably embodiment of the present invention
And polyvalent alcohol, sulfonate functional polyether Glycols type hydrophilic chain extender, polyisocyanates and/or solvent be as described above
's.
Do not included according to the one of the present invention more preferably embodiment, the method that the present invention prepares sulfonic waterborne polyurethane emulsion
Add organic solvent, such as the step of acetone, DMF and/or 1-METHYLPYRROLIDONE.
Do not included according to the one of the present invention more preferably embodiment, the method that the present invention prepares sulfonic waterborne polyurethane emulsion
The step of removing organic solvent, such as being evaporated under reduced pressure.
Brief description of the drawings
Fig. 1 is the reaction temperature that the demonstrated of non-limiting example 1 to 5 of the present invention prepares sulfonic waterborne polyurethane emulsion
Write music line and raw material addition flow.
Embodiment
The present invention is further described specifically with embodiment below in conjunction with accompanying drawing.It is necessarily pointed out that with
Lower embodiment is served only for that the present invention is described further, it is impossible to is interpreted as limiting the scope of the invention, the field
Person skilled in the art makes some nonessential modifications and adaptations according to the invention described above content to the present invention, still falls within the present invention
Protection domain.Before some non-limiting examples of the present invention are discussed, it should be appreciated that the present invention is not limited in its application
Shown in herein and the details of specific non-limiting example discussed, because the present invention can have other embodiment.In addition,
Term herein for discussing the present invention, which is in order at, to be described and unrestricted purpose.Again in addition, except as otherwise noted, otherwise
The discussion of similar numeral refers to similar key element below.
All numerals such as expression contents, ratio, physical features used in this specification and claim should
It is interpreted as modifying through term " about " in all cases.Therefore, unless the contrary indication, it is otherwise special in description below and application
Characteristic that the visual present invention of numerical value illustrated in sharp scope reaches out for and/or required and change.At least, and be not intended to by etc.
The application of effect principle is limited in claim, each numerical parameter at least should according to the number of disclosed effective digital and
Explained by the general rounding-off technology of application.
All scopes disclosed herein should be understood as covering any and all underrange included in it.Citing
For, " 1 to 10 " described scope should be regarded as comprising any and all underrange between minimum value 1 and maximum 10 and comprising most
Big value 1 and maximum 10；That is, all times for being started with 1 or the minimum value more than 1 and being terminated with 10 or the maximum less than 10
Scope, such as：1 to 6.7,3.2 to 8.1 or 5.5 to 10, and any numeral in the range of this, such as：2.6th, 4.7 or 7.3.
Embodiment 1
Weigh the polyadipate ethylene glycol butanediol ester (molecular weight of the vacuum dried dewater treatments of 300g：And 28g 2,000)
Double-Isosorbide-5-Nitrae-(2- hydroxy propyloxy groups) -2- propylbutyl ether sodium sulfonates stir and are heated to 60 DEG C, weigh the different Fo Er of 61.71g
Ketone diisocyanate (IPDI), 95 DEG C of progress polymerisations of keeping temperature, the reaction time is 4 hours, reacts to NCO content and reaches
Theoretical value, polyurethane prepolymer is made；Stir speed (S.S.) is improved, 470g water is directly added dropwise to the polyurethane prepolymer, emulsification 10
After minute turns aqueous phase, 1.6g ethylenediamines are added, sulfonic waterborne polyurethane emulsion is made, 5 weight % are added before film, and (being based on should
The total solid content meter of emulsion) aliphatic isocyanates in order crosslinking agent to lift the hydrolytic resistance of dry film, the temperature of above-mentioned reaction is bent
Line and flow are as shown in Figure 1.
Embodiment 2
Weigh the poly adipate succinic acid ester (molecular weight of vacuum dried dewater treatment：And polyadipate second two 2,000)
Alcohol butanediol ester (molecular weight：2,000) double -1,4- (2- hydroxy propyloxy groups) -2- propylbutyl ether sulfonic acid of common 300g and 61.09g
Sodium stirs and is heated to 60 DEG C, weighs 97.97g IPDIs (IPDI), adds 0.04g tin dilaurates two
Butyl tin catalyst, 95 DEG C of progress polymerisations of keeping temperature, the reaction time is 2 hours, reacts to NCO content and reaches theoretical
Value, polyurethane prepolymer is made；Stir speed (S.S.) is improved, 1100g water is directly added dropwise to the polyurethane prepolymer, emulsified 10 minutes
After turning aqueous phase, 2.05g diethylenetriamines and 7.06g ethylenediamines are added, sulfonic waterborne polyurethane emulsion is made, is added before film
5 weight % (the total solid content meter based on the emulsion) aliphatic isocyanates in order crosslinking agent to lift the hydrolytic resistance of dry film, on
Temperature curve and the flow for stating reaction are as shown in Figure 1.
Embodiment 3
Weigh the polytetramethylene ether glycol (molecular weight of the vacuum dried dewater treatments of 200g：And 41.43g double -1,2,000)
4- (2- hydroxy propyloxy groups) -2- propylbutyl ether sodium sulfonates stir and are heated to 60 DEG C, weigh 74.22g1, the methylenes of 6- six
Group diisocyanate (HDI), 0.02g dibutyltin dilaurate catalysts are added, 95 DEG C of keeping temperature carries out polymerisations, instead
It is 1.5 hours between seasonable, reacts to NCO content and reach theoretical value, polyurethane prepolymer is made；Stir speed (S.S.) is improved, by 282g
Water is directly added dropwise to the polyurethane prepolymer, and emulsification adds 2g polyoxypropylene triamines and 21g isophorones after turning within 10 minutes aqueous phase
Diamines, sulfonic waterborne polyurethane emulsion is made, the carbon that 5 weight % (the total solid content meter based on the emulsion) are added before film is sub-
For acid amides crosslinking agent to lift the hydrolytic resistance of dry film, the temperature curve and flow of above-mentioned reaction are as shown in Figure 1.
Embodiment 4
Weigh the poly-lactone polyol (molecular weight of the vacuum dried dewater treatments of 300g：And double -1,4- (the 2- of 73g 2,000)
Hydroxyl-oxethyl) -2- ethoxy butane potassium sulfonates stir and are heated to 60 DEG C, weigh 83.6g diphenyl methanes 4,4- bis-
Isocyanates (MDI), 95 DEG C of progress polymerisations of keeping temperature, the reaction time is 2 hours, reacts to NCO content and reaches theoretical
Value, polyurethane prepolymer is made；Stir speed (S.S.) is improved, 1570g water is directly added dropwise to the polyurethane prepolymer, emulsified 10 minutes
After turning aqueous phase, 13.2g ethylenediamines and 9.8g m-xylene diamines are added, sulfonic waterborne polyurethane emulsion is made, is added before film
The U.S. crosslinking agent of resistance to ware of weight 5% (the total solid content meter based on the emulsion) to lift the hydrolytic resistance of dry film, above-mentioned reaction
Temperature curve and flow are as shown in Figure 1.
Embodiment 5
Weigh the PPG (molecular weight of the vacuum dried dewater treatments of 300g：And double -1,4- (the 2- hydroxyls of 52g 2,000)
Base oxethyl) -2- ethoxy butane sodium sulfonates stir and are heated to 60 DEG C, weigh 71.1g toluene di-isocyanate(TDI)s
(TDI), 95 DEG C of progress polymerisations of keeping temperature, the reaction time is 2.5 hours, reacts to NCO content and reaches theoretical value, is made
Polyurethane prepolymer；Stir speed (S.S.) is improved, 1320g water is directly added dropwise to the polyurethane prepolymer, emulsification turns aqueous phase in 10 minutes
Afterwards, 12.6g hexamethylene diamines and 8.8g phenylenediamines are added, sulfonic waterborne polyurethane emulsion is made, 5 weight % (bases are added before film
In the total solid content meter of the emulsion) carbon Asia acid amides crosslinking agent can lift the hydrolytic resistance of dry film, the temperature curve of above-mentioned reaction
And flow is as shown in Figure 1.
Properties of product are tested
I. the measure of solid content
Dry surface plate is taken, claims its weight to be designated as m, 1.5~2.0g aqueous polyurethane emulsions is then weighed and is laid in table
Weighed in the ware of face as m0, 120 DEG C of dryings 2 hours are put into baking oven, taking-up, which is weighed, is designated as m1, solid content is in the following manner
Calculate：
Solid content (%)=[(m1-m)/m0] x100%.
Ii. hydrolytic resistance
Dry film is subjected to ISO 1419:1995 hydrolytic resistances test (Jungle test), humidity 95%, temperature 70 C, put
Put one week detection physical property conservation rate.
Iii. stability of emulsion determines
100g emulsions are deposited under room temperature (25 DEG C), have seen whether Precipitation week about, are separated out used in precipitation
Time is longer, and stability is better.
Table 1:The test result of the polyaminoester emulsion of embodiment 1 to 5
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvement and deformation can also be made, these are improved and deformation
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of sulfonic waterborne polyurethane emulsion, it is characterized in that, gather comprising polyisocyanates, polyvalent alcohol, sulfonate functional
Ether binary alcohol type hydrophilic chain extender and solvent.
2. a kind of sulfonic waterborne polyurethane emulsion according to claim 1, it is characterized in that, the sulfonate functional polyethers
Binary alcohol type hydrophilic chain extender has structure shown in formula I：
Wherein, R1For the three-level alkyl with 2 to 14 C atoms；M+For the metal ion of positively charged；And R2To R5Independently of one another
For hydrogen or the alkyl with 1 to 6 C atom.
3. a kind of sulfonic waterborne polyurethane emulsion according to claim 1, it is characterized in that, it is water-based based on the sulfonic acid type
The total solid content meter of polyaminoester emulsion, in terms of weight percentage, the sulfonate functional polyether Glycols type hydrophilic chain extender
Content be 1~35%.
4. a kind of sulfonic waterborne polyurethane emulsion according to any one of claim 1-3, it is characterized in that, the polyisocyanate
Cyanate includes diisocyanate, and the diisocyanate includes toluene di-isocyanate(TDI) (TDI), the isocyanide of Isosorbide-5-Nitrae-tetramethylene two
Acid esters, 1,6- hexamethylene diisocyanates (HDI), the dimethylene diisocyanates of 1,12- ten, the isocyanides of hexamethylene -1,3- two
Acid esters, hexamethylene -1,4- diisocyanate, IPDI (IPDI), diphenyl methane 4,4- diisocyanate
(MDI), double-hexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), polymethylene polyphenyl isocyanic acid
Ester (PAPI), XDI (XDI), naphthalene -1,5- diisocyanate (NDI), the isocyanic acid of methylcyclohexyl two
One or more of combinations in ester (HTDI), tetramethylxylylene diisocyanate (TMXDI).
5. a kind of sulfonic waterborne polyurethane emulsion according to any one of claim 1-3, it is characterized in that, based on described
The total solid content meter of sulfonic waterborne polyurethane emulsion, in terms of weight percentage, the content of the polyisocyanates for 5~
35%.
6. a kind of sulfonic waterborne polyurethane emulsion according to any one of claim 1-3, it is characterized in that, it is described poly- more
First alcohol includes PEPA, poly-lactone polyol, PPG, polycarbonate polyol, polythiaether polyol, polyethers and gathered
One or more of combinations in the mixed polymers polyalcohol of ester.
7. a kind of sulfonic waterborne polyurethane emulsion according to any one of claim 1-3, it is characterized in that, based on described
The total solid content meter of sulfonic waterborne polyurethane emulsion, in terms of weight percentage, the content of the polyvalent alcohol for 45~
80%.
8. a kind of sulfonic waterborne polyurethane emulsion according to any one of claim 1-3, it is characterized in that, in addition to urge
One or more in agent, small molecule chain extender, hydrophilic chain extender, crosslinking agent, the catalyst include tertiary amine catalyst,
One or more of combinations in organotin catalysts, non-tin metal compound catalyst；The small molecule chain extender includes
Ethylenediamine, hexamethylene diamine, phenylenediamine, diethanol amine, polyoxypropylene triamine, diethylenetriamine, IPD, isophthalic diformazan
One or more of combinations in amine, methyl diethanolamine；The hydrophilic chain extender includes dihydromethyl propionic acid, dihydroxymethyl
One kind in butyric acid, dihydroxy half ester, second diaminourea ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium, diaminopropionic acid, diaminobutyric acid
Or several combination；The crosslinking agent includes aliphatic isocyanates in order, polyaziridine, water-base epoxy based cross-linker, carbon Asia acid amides
One or more of combinations in crosslinking agent, melamine formaldehyde resin (U.S. resistance to ware).
9. a kind of glued membrane, it is characterized in that, it is made as the sulfonic waterborne polyurethane emulsion any one of claim 1-8.
10. a kind of method for preparing the sulfonic waterborne polyurethane emulsion any one of claim 1-8, it is characterized in that,
Comprise the following steps：
Mix polyvalent alcohol and sulfonate functional polyether Glycols type hydrophilic chain extender forms mixture；
Polyisocyanates is added in the mixture, so that polyurethane prepolymer is made；And
Solvent is added in the polyurethane prepolymer, emulsifies the polyurethane prepolymer so that the water-based poly- ammonia of sulfonic acid type is made
Ester emulsion.
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| CN108178824A (en) * | 2018-01-31 | 2018-06-19 | 长春市三化实业有限责任公司 | A kind of sulfonic waterborne polyurethane emulsion and its non-solvent preparation |
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| CN109734871A (en) * | 2018-12-30 | 2019-05-10 | 沈阳化工研究院有限公司 | A kind of low water absorbable, high solids content polyaminoester emulsion preparation method |
| CN109734866A (en) * | 2018-12-13 | 2019-05-10 | 华南理工大学 | A kind of high-performance anionic and nonionic type aqueous polyurethane dispersion and preparation method thereof |
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| CN114517051A (en) * | 2022-03-02 | 2022-05-20 | 万华化学集团股份有限公司 | Waterborne polyurethane-urea dispersion, preparation method and application thereof |
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| CN112251070A (en) * | 2020-10-22 | 2021-01-22 | 梁贻波 | Environment-friendly water-based ink and preparation method thereof |
| CN114517051A (en) * | 2022-03-02 | 2022-05-20 | 万华化学集团股份有限公司 | Waterborne polyurethane-urea dispersion, preparation method and application thereof |
| CN114517051B (en) * | 2022-03-02 | 2023-12-19 | 万华化学集团股份有限公司 | Aqueous polyurethane-urea dispersion, preparation method and application thereof |
| CN115403735A (en) * | 2022-10-13 | 2022-11-29 | 西安交通大学 | Sulfonic acid type waterborne polyurethane emulsion and preparation method thereof |
| CN115403735B (en) * | 2022-10-13 | 2024-01-26 | 西安交通大学 | Sulfonic acid type aqueous polyurethane emulsion and preparation method thereof |
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