CN107446105B

CN107446105B - Sulfonic acid type waterborne polyurethane emulsion, product and preparation method thereof

Info

Publication number: CN107446105B
Application number: CN201710622512.5A
Authority: CN
Inventors: 林棋灿
Original assignee: COATING FINE CHEMICALS (KUNSHAN) CO LTD
Current assignee: COATING FINE CHEMICALS (KUNSHAN) CO LTD
Priority date: 2017-07-28
Filing date: 2017-07-28
Publication date: 2020-06-19
Anticipated expiration: 2037-07-28
Also published as: CN107446105A

Abstract

The invention discloses a sulfonic acid type aqueous polyurethane emulsion, a product and a preparation method thereof, which are characterized by comprising polyisocyanate, polyol, sulfonate functional polyether glycol type hydrophilic chain extender and solvent, and the sulfonic acid type aqueous polyurethane emulsion has the advantages that the dosage of organic solvent, carboxylic acid and neutralizer can be greatly reduced, and the preparation method is simple and environment-friendly; the sulfonic acid type waterborne polyurethane emulsion also has good stability, so that a glue film prepared from the sulfonic acid type waterborne polyurethane emulsion has better hydrolysis resistance and yellowing resistance.

Description

Sulfonic acid type waterborne polyurethane emulsion, product and preparation method thereof

Technical Field

The invention relates to a sulfonic acid type waterborne polyurethane emulsion, a product thereof and a preparation method thereof, belonging to the technical field of polymer materials.

Background

The polyurethane is widely applied to the fields of coatings, adhesives, printing ink, leather processing, textiles and the like, has excellent performance, still adopts a large amount of organic solvent polyurethane in the industry at present to reduce the system viscosity or dissolve reactants, the common organic solvent mainly comprises acetone, N-dimethylformamide and/or N-methylpyrrolidone and the like, the acetone is partially or completely removed through a reduced pressure distillation mode after the preparation of the aqueous polyurethane emulsion is finished, and the N, N-dimethylformamide and N-methylpyrrolidone generally remain in the emulsion due to relatively high boiling points. Therefore, the current industrial preparation of aqueous polyurethane emulsion is not a real aqueous emulsion system without organic solvent, i.e. it has a certain degree of Volatile Organic Compound (VOC) release during preparation and use, which poses a serious threat to the health of constructors and consumers, and the governments of various countries have also made legislation to limit the content of volatile organic compounds or Harmful Air Pollutants (HAP) in polyurethane products.

The aqueous polyurethane emulsion takes water as a dispersion medium, has the advantages of no toxicity, no flammability, environmental friendliness, low cost and the like, and has become an important research direction in the field of polyurethane at present. The aqueous polyurethane emulsion keeps the characteristics of high glossiness, high strength, high wear resistance, high elasticity, high adhesiveness, low temperature resistance, fatigue resistance and the like of the traditional organic solvent type polyurethane, has the advantages of safe transportation, good operation environment, irrelevant viscosity to polymer molecular weight and the like, and simultaneously avoids the problem of environmental pollution caused by a large amount of volatile organic solvents generated in the use process of the organic solvent type polyurethane.

The traditional aqueous polyurethane emulsion is prepared by the components of oligomer dihydric alcohol, diisocyanate, a hydrophilic chain extender, a micromolecule chain extender and the like through addition polymerization and water dispersion, and compared with the organic solvent type polyurethane emulsion, the synthesis of the aqueous polyurethane emulsion has the key point of using the hydrophilic chain extender besides different used dispersion media, and the hydrophilic chain extender can introduce hydrophilic groups into a polyurethane molecular structure so that the aqueous polyurethane emulsion has good dispersibility or self-emulsifying property. For example, the prior art US 5470907 a and US 6017998A disclose a method for preparing an aqueous polyurethane emulsion using dimethylolpropionic acid (DMPA) as a hydrophilic chain extender; CN 101475678A also discloses a preparation method of the aqueous polyurethane emulsion which takes ethylene diamine ethyl sodium sulfonate (AAS) as a main hydrophilic chain extender; US 4870129A discloses a method for preparing an aqueous polyurethane emulsion using dimethylolpropionic acid and ethylenediamine ethanesodium sulfonate as co-hydrophilic chain extenders; US 2006/0036054 a1 discloses a process for the preparation of sulfonate-functional polyester polyols, which can be used in the soft segment of polyurethanes.

At present, anionic hydrophilic chain extenders related to aqueous polyurethane emulsions are mainly divided into two types, namely carboxylic acid type chain extenders and sulfonate type chain extenders, and compared with carboxylic acid type chain extenders (such as DMPA/DMBA), the sulfonate type chain extenders have better hydrophilicity, so that compared with the carboxylic acid type chain extenders, when polyurethane with the same hydrophilicity is prepared, the molar amount of the sulfonate type chain extenders is less, and because ions on a polyurethane chain are reduced, electrostatic repulsion force is weakened, the hydration volume cannot be rapidly increased, so that the viscosity of a system is increased, and the sulfonate type chain extenders are more favorable for preparing aqueous polyurethane emulsions with high solid content.

In addition, the use of a carboxylic acid type chain extender (e.g., DMPA/DMBA) additionally provides a neutralization salt formation step prior to the water emulsification step. The neutralizing agent widely used at present is triethylamine, and after the neutralization and the salt formation by the triethylamine, triethylamine still possibly remains in the aqueous polyurethane emulsion prepared by emulsification, so that the aqueous polyurethane emulsion has the defect of unpleasant and pungent odor, and the triethylamine can also be decomposed and volatilized in the storage process of the emulsion, thereby reducing the stability of the aqueous polyurethane emulsion. Compared with the prior art, the sulfonate chain extender is neutral, so a neutralizer is not required to be added in the emulsion dispersing process, and the problems of unpleasant and pungent smell or decomposition and volatilization can be effectively avoided; and moreover, the sulfonate chain extender has good storage stability and is not influenced by external environment (such as temperature), so that the prepared aqueous polyurethane emulsion has small deviation on physical properties, and the aqueous polyurethane emulsion product has higher reproducibility and stability, can effectively monitor the quality and is beneficial to mass production.

However, in the sulfonate chain extender used in the prior art, the viscosity of the system still needs to be adjusted by acetone in the dispersion process, and in order to meet the requirements of the current environment-friendly polymer material, the acetone needs to be removed by an additional reduced pressure distillation step after the sulfonate waterborne polyurethane product is prepared. However, the above-mentioned process for separating acetone is complicated, time-consuming and increases the manufacturing cost, and the acetone removed by vacuum distillation still has a concern about VOC emission, i.e., the existing process for producing aqueous polyurethane emulsion is not a full environmental protection process.

Disclosure of Invention

The invention aims to provide an environment-friendly sulfonic acid type aqueous polyurethane emulsion, a product thereof and a manufacturing method thereof; the invention further provides the sulfonic acid type aqueous polyurethane emulsion without adding any organic solvent, carboxylic acid and/or neutralizing agent in the preparation process, the product thereof and the preparation method thereof. The sulfonic acid type aqueous polyurethane emulsion and the preparation method thereof provided by the invention not only achieve the purpose of environmental protection from the manufacturing end, but also can be widely used in products such as paint, adhesive and the like.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a sulfonic acid type aqueous polyurethane emulsion comprises polyisocyanate, polyol, sulfonate functional polyether glycol type hydrophilic chain extender and solvent.

The components are described in detail below.

Polyisocyanate, and a process for producing the same

The sulfonic acid type aqueous polyurethane emulsion of the present invention is not particularly required for polyisocyanate. The polyisocyanates suitable for use in the present invention preferably comprise diisocyanates comprising one or more of the following compositions: toluene Diisocyanate (TDI), 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, isophorone diisocyanate (IPDI), diphenylmethane 4, 4-diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), 1, 6-Hexamethylene Diisocyanate (HDI), polymethylene polyphenyl isocyanates (PAPI), Xylylene Diisocyanate (XDI), naphthalene-1, 5-diisocyanate (NDI), methylcyclohexyl diisocyanate (HTDI), tetramethylxylylene diisocyanate (TMXDI), and mixtures thereof. More preferred polyisocyanates are isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), 1, 6-Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane 4, 4-diisocyanate (MDI), or Toluene Diisocyanate (TDI).

According to an embodiment of the present invention, the content of the polyisocyanate is 5 to 35% by weight, based on the total solid content of the sulfonic acid-type aqueous polyurethane emulsion, as follows: 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, or 34%, more preferably 10 to 30%, and still more preferably 15 to 25%.

Polyol, polyol and polyol mixture

The sulfonic acid type aqueous polyurethane emulsion of the present invention is not particularly required for the polymeric polyol. The polymeric polyol applicable to the invention comprises one or more of the following polymeric polyols: polyester polyols, polylactone polyols, polyether polyols, polycarbonate polyols, polythioether polyols, mixed polymer polyols of polyethers and polyesters, and mixtures thereof. The polyhydric alcohol preferably comprises polyethylene glycol, polypropylene oxide glycol, polytetrahydrofuran ether glycol, polybutylene succinate, polyhexamethylene adipate, polybutylene adipate, polyethylene glycol adipate or polypropylene carbonate glycol, and can be selected according to different finished product characteristics.

According to an embodiment of the invention, the polymeric polyol has a molecular weight of 600 to 5,000, such as: 800. 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, or 4800, more preferably 1,000 to 4,000.

According to an embodiment of the present invention, the content of the polymeric polyol is 45-80% by weight, based on the total solid content of the sulfonic acid-type aqueous polyurethane emulsion, as follows: 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, or 74%, more preferably 50 to 75%, and still more preferably 55 to 70%.

Sulfonate functional polyether glycol type hydrophilic chain extender

The sulfonate functional polyether glycol type hydrophilic chain extender contained in the sulfonic acid type aqueous polyurethane emulsion has a structure as shown in formula I:

I，

wherein R is¹Is a tertiary hydrocarbon group having 2 to 14C atoms, such as an alkyl group having 2 to 14C atoms, more preferably a tertiary linear hydrocarbon group having 2 to 14C atoms, such as a linear alkyl group having 2 to 14C atoms, still more preferably a tertiary linear hydrocarbon group having 2 to 6C atoms, such as a linear alkyl group having 2 to 6C atoms; m⁺Is a positively charged metal ion, more preferably an alkali metal ion, more preferably a sodium or potassium ion; and R is²To R⁵Each independently hydrogen or alkyl having 1 to 6C atoms, more preferably each independently hydrogen or straight chain alkyl having 1 to 6C atoms, more preferably R²And R³Each independently of the others is propyl or butyl and R⁴And R⁵Is methyl or ethyl.

According to a more preferred embodiment of the present invention, the sulfonate-functional polyether glycol type hydrophilic chain extender has a Bis-1,4- (2-hydroxypropoxy) -2-propoxybutanesulfonate structure (Bis-1, 4- (2-hydroxypropoxy) -2-propoxybutane sulfonate) as shown in formula II.

II，

Wherein M is⁺Is a positively charged metal ion, more preferably an alkali metal ion, and even more preferably a sodium or potassium ion. According to a more preferred embodiment of the present invention, the sulfonate-functional polyether glycol-type hydrophilic chain extender comprises one or more of the following compositions: sodium bis-1,4- (2-hydroxypropoxy) -2-propoxybutanesulfonate (sodium bis-1,4- (2-hydroxypropoxy) -2-propoxybutanesulfonate),Potassium bis-1,4- (2-hydroxyethoxy) -2-ethoxybutane sulfonate, and sodium bis-1,4- (2-hydroxyethoxy) -2-ethoxybutane sulfonate.

According to an embodiment of the present invention, the content of the sulfonate-functional polyether glycol-type hydrophilic chain extender is 1 to 35% by weight, based on the total solid content of the sulfonic acid-type aqueous polyurethane emulsion, such as: 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, or 34%, more preferably 5 to 25%, and still more preferably 10 to 20%.

The sulfonate functional polyether glycol type hydrophilic chain extender defined by the invention has the beneficial effects that: compared with the common sulfamate type hydrophilic chain extender, the sulfonate functional polyether glycol type hydrophilic chain extender has the advantages that the reaction of hydroxyl groups of the sulfonate functional polyether glycol type hydrophilic chain extender and polyisocyanate is milder in the reaction process, so that the viscosity of the formed prepolymer is not suddenly increased, the reaction can be controlled more easily, and in a better condition, a large amount of acetone is not required to be added to reduce the system viscosity.

On the other hand, compared with other sulfonate-functional polyether glycol type hydrophilic chain extenders, the sulfonate-functional polyether glycol type hydrophilic chain extender defined above has lower molecular weight, so that a sulfonic acid group can be introduced by adding a small amount, so as to reduce the manufacturing cost; in addition, in the process of preparing the sulfonic acid type aqueous polyurethane emulsion, the sulfonate functional polyether glycol type hydrophilic chain extender is selected, so that a large amount of organic solvent is avoided, an additional step of neutralizing and salifying is not needed, a complicated procedure of impurity removal is omitted, and the synthesis process is simplified.

Catalyst, and process for producing the same

The sulfonic acid type aqueous polyurethane emulsion of the present invention may further include a catalyst as required. The catalyst suitable for the sulfonic acid type aqueous polyurethane emulsion comprises one or more of the following components: tertiary amine catalysts, organotin catalysts, or non-tin metal compound catalysts. Stannous octoate or dibutyltin dilaurate are more preferred.

According to an embodiment of the present invention, the content of the catalyst is 0 to 200ppm in ppm by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion, such as: 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, or 190ppm, more preferably 0 to 150ppm, and still more preferably 0 to 100 ppm.

Micromolecular chain extender

The sulfonic acid type aqueous polyurethane emulsion can additionally comprise a micromolecular chain extender according to requirements. According to an embodiment of the present invention, the small molecule chain extender includes one or more of the following small molecule chain extenders: ethylenediamine, hexamethylenediamine, phenylenediamine, diethanolamine, polyoxypropylene triamine, diethylenetriamine, isophoronediamine, m-xylylenediamine, or methyldiethanolamine.

According to an embodiment of the present invention, the content of the small molecule chain extender is 0.1 to 20% by weight, based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion, such as: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%, more preferably 0.5 to 15%, and still more preferably 1 to 10%.

Other hydrophilic chain extenders

The sulfonic acid type aqueous polyurethane emulsion also comprises other hydrophilic chain extenders of non-sulfonate functional polyether glycol type hydrophilic chain extenders. According to an embodiment of the present invention, the other hydrophilic chain extenders include one or more of the following hydrophilic chain extenders: dimethylol propionic acid, dimethylol butyric acid, dihydroxy half ester, ethylene diamino ethane sodium sulfonate, diamino benzene sodium sulfonate, diamino propionic acid, or diamino butyric acid.

According to an embodiment of the present invention, the content of the other hydrophilic chain extender is 0.1 to 20% by weight, based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion, such as: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%, more preferably 0.5 to 15%, and still more preferably 1 to 10%.

Crosslinking agent

The sulfonic acid type aqueous polyurethane emulsion can additionally comprise a cross-linking agent according to needs so as to improve the cross-linking density and increase the hydrolysis resistance of the aqueous polyurethane emulsion. According to an embodiment of the invention, the cross-linking agent comprises one or more of the following cross-linking agent compositions: aliphatic isocyanates, polyaziridines, waterborne epoxy crosslinkers, carbodiimide crosslinkers, or melamine-formaldehyde resins (melamine). The carbodiimide cross-linking agent is more preferably a GSI type carbodiimide.

According to an embodiment of the present invention, the crosslinking agent content is 0 to 20% in weight percent based on the total amount of the sulfonic acid type aqueous polyurethane emulsion, such as: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%, more preferably 2 to 15%, and still more preferably 5 to 10%.

A solvent

The solvent suitable for the sulfonic acid type aqueous polyurethane emulsion of the present invention includes water, and preferably the solvent consists essentially of water.

According to an embodiment of the present invention, the solvent content is 55 to 80% by weight, based on the total weight of the sulfonic acid-type aqueous polyurethane emulsion, such as: 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, or 78%, preferably 60 to 75%, and more preferably 65 to 70%.

According to a more preferred embodiment of the present invention, the organic solvent is contained in the solvent in an amount of 5.0% by weight or less, based on the total weight of the sulfonic acid type aqueous polyurethane emulsion, 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 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, more preferably 1.0% or less, more preferably completely free of any organic solvent.

According to a more preferred embodiment of the present invention, the solvent contains acetone, N-dimethylformamide and/or N-methylpyrrolidone in an amount of 5.0% by weight or less, based on the total weight of the sulfonic acid type aqueous polyurethane emulsion, 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 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, more preferably 1.0% or less, more preferably completely free of any acetone, N-dimethylformamide and/or N-methylpyrrolidone.

Therefore, the sulfonic acid type aqueous polyurethane emulsion has the following beneficial effects:

a) the water-based polyurethane emulsion adopts sulfonate as a hydrophilic group, so that the neutralization reaction additionally related to a common carboxylate component can be omitted, and because the polyurethane prepolymer formed in the emulsion comprises the sulfonate hydrophilic group, the polyurethane prepolymer has hydrophilicity, so that the polyurethane prepolymer can be directly dissolved in water, and acetone is not additionally added for viscosity reduction, so that the sulfonic acid-type water-based polyurethane emulsion disclosed by the invention is more in line with the environment-friendly requirement. In addition, because the polyurethane prepolymer formed by the aqueous polyurethane emulsion of the invention is soluble in water, when only water is used as a solvent, the stirring speed can be increased by using the existing stirrer, and a homogenizer is not required to be additionally used, so that the sulfonic acid type aqueous polyurethane emulsion can be successfully prepared.

b) The straight chain type sulfonate functional polyether glycol type hydrophilic chain extender preferably used in the sulfonic acid type aqueous polyurethane emulsion can increase the flexibility of a formed adhesive film.

c) The sulfonic acid type aqueous polyurethane emulsion further comprises a cross-linking agent according to requirements, so that the cross-linking density of the originally water-soluble polyurethane can be improved, and the hydrolysis resistance is improved.

d) The sulfonic acid type waterborne polyurethane emulsion is particularly suitable for products such as coating, adhesive and the like, and has strong functionality and wide application prospect.

The invention also provides an adhesive film, which is used for printing ink resin, a coating, a bottom material, hot melt adhesive and adhesive resin of a soft material, wherein the adhesive film is prepared from the sulfonic acid type waterborne polyurethane emulsion.

The invention also provides a method for preparing the sulfonic acid type aqueous polyurethane emulsion, which comprises the following steps:

1. mixing a polyol and a sulfonate functional polyether glycol type hydrophilic chain extender;

2. adding a polyisocyanate to the mixture to produce a polyurethane prepolymer; and

3. adding a solvent into the polyurethane prepolymer, and emulsifying the polyurethane prepolymer to prepare the sulfonic acid type aqueous polyurethane emulsion.

According to an embodiment of the present invention, the mixing step in step 1 is preferably performed at a temperature of 50 ℃ or higher, more preferably 60 ℃ or higher.

According to an embodiment of the present invention, the temperature in step 2 is preferably 50 ℃ or higher, more preferably 65 to 95 ℃, and the reaction time is within 1 to 7 hours, preferably within 2 to 5 hours, so as to obtain the polyurethane prepolymer product.

According to an embodiment of the invention, a catalyst as described above may be added in step 2.

According to an embodiment of the present invention, in the emulsification step in the step 3, the selected solvent includes water, and preferably, the selected solvent substantially consists of water.

According to an embodiment of the present invention, a small molecule chain extender, such as ethylenediamine, as described above, may be added after the emulsification step of step 3.

According to a more preferred embodiment of the present invention, the polyhydric alcohol, the sulfonate-functional polyether glycol-type hydrophilic chain extender, the polyisocyanate and/or the solvent involved in the preparation of the sulfonic acid-type aqueous polyurethane emulsion of the present invention are as described above.

According to a more preferred embodiment of the present invention, the method for preparing the sulfonic acid type aqueous polyurethane emulsion according to the present invention does not include a step of adding an organic solvent such as acetone, N-dimethylformamide and/or N-methylpyrrolidone.

According to a more preferred embodiment of the present invention, the process for producing a sulfonic acid type aqueous polyurethane emulsion of the present invention does not comprise a step of removing the organic solvent, for example, distillation under reduced pressure.

Drawings

FIG. 1 is a diagram showing the reaction temperature profile and the raw material addition flow for preparing a sulfonic acid type aqueous polyurethane emulsion as exemplified in non-limiting examples 1 to 5 of the present invention.

Detailed Description

The invention is further described in detail below with reference to the drawings and examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of the invention in light of the above teachings, while still remaining within the scope of the invention. Before discussing several non-limiting embodiments of the invention, it is to be understood that the invention is not limited in its application to the details of the particular non-limiting embodiments shown and discussed herein, as the invention may have other embodiments. Furthermore, the terminology used herein for the purpose of describing the invention is for the purpose of description and not of limitation. Still further, unless otherwise indicated, the following discussion of like numbers refers to like elements.

All numbers expressing quantities, proportions, physical characteristics, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending upon the desired properties and/or characteristics sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

All ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a range of "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10 and include the maximum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more than 1 and ending with a maximum value of 10 or less than 10, for example: 1 to 6.7, 3.2 to 8.1, or 5.5 to 10, and any number within this range, for example: 2.6, 4.7 or 7.3.

Example 1

Weighing 300g of polyethylene glycol butanediol adipate (molecular weight: 2,000) subjected to vacuum drying and dehydration treatment and 28g of bis-1,4- (2-hydroxypropoxy) -2-propoxybutanesulfonate, uniformly stirring, heating to 60 ℃, weighing 61.71g of isophorone diisocyanate (IPDI), keeping the temperature at 95 ℃ for polymerization reaction for 4 hours, and reacting until the NCO content reaches a theoretical value to obtain a polyurethane prepolymer; the stirring rate is increased, 470g of water is directly dripped into the polyurethane prepolymer, after emulsification for 10 minutes and water phase conversion, 1.6g of ethylenediamine is added to prepare sulfonic acid type aqueous polyurethane emulsion, 5 wt% (based on the total solid content of the emulsion) of aliphatic isocyanate crosslinking agent is added before film coating to improve the hydrolysis resistance of a dry film, and the temperature curve and the flow of the reaction are shown in figure 1.

Example 2

Weighing 300g of polybutylene adipate (molecular weight: 2,000) and 61.09g of bis-1,4- (2-hydroxy propoxy) -2-propoxy butane sodium sulfonate which are subjected to vacuum drying and dehydration treatment, uniformly stirring, heating to 60 ℃, weighing 97.97g of isophorone diisocyanate (IPDI), adding 0.04g of dibutyltin dilaurate catalyst, keeping the temperature at 95 ℃ for carrying out polymerization reaction for 2 hours, and reacting until the NCO content reaches a theoretical value to obtain a polyurethane prepolymer; the stirring speed is improved, 1100g of water is directly dripped into the polyurethane prepolymer, after emulsification is carried out for 10 minutes and water phase conversion is carried out, 2.05g of diethylenetriamine and 7.06g of ethylenediamine are added to prepare sulfonic acid type aqueous polyurethane emulsion, 5 wt% (based on the total solid content of the emulsion) of aliphatic isocyanate crosslinking agent is added before film coating to improve the hydrolysis resistance of a dry film, and the temperature curve and the flow of the reaction are shown in figure 1.

Example 3

Weighing 200g of vacuum drying and dehydrating poly-tetramethyl ether glycol (molecular weight: 2,000) and 41.43g of bis-1,4- (2-hydroxy propoxy) -2-propoxy butane sodium sulfonate, uniformly stirring, heating to 60 ℃, weighing 74.22g of 1, 6-Hexamethylene Diisocyanate (HDI), adding 0.02g of dibutyltin dilaurate catalyst, keeping the temperature at 95 ℃ for polymerization reaction for 1.5 hours, and reacting until the NCO content reaches a theoretical value to obtain a polyurethane prepolymer; the stirring rate is increased, 282g of water is directly added into the polyurethane prepolymer in a dropwise manner, 2g of polyoxypropylene triamine and 21g of isophorone diamine are added after emulsification is carried out for 10 minutes to form a water phase, a 5 wt% (based on the total solid content of the emulsion) of a carbodiimide crosslinking agent is added before film coating so as to improve the hydrolysis resistance of a dry film, and the temperature curve and the flow of the reaction are shown in figure 1.

Example 4

Weighing 300g of vacuum drying dehydration treated polylactone polyol (molecular weight: 2,000) and 73g of potassium bis-1,4- (2-hydroxyethoxy) -2-ethoxybutane sulfonate, uniformly stirring, heating to 60 ℃, weighing 83.6g of diphenylmethane 4, 4-diisocyanate (MDI), keeping the temperature at 95 ℃ for polymerization reaction for 2 hours, and reacting until the NCO content reaches a theoretical value to obtain a polyurethane prepolymer; the stirring speed is increased, 1570g of water is directly dripped into the polyurethane prepolymer, after emulsification for 10 minutes and water phase conversion, 13.2g of ethylenediamine and 9.8g of m-xylylenediamine are added to prepare the sulfonic acid type aqueous polyurethane emulsion, 5 percent by weight (based on the total solid content of the emulsion) of melamine cross-linking agent is added before film coating to improve the hydrolysis resistance of a dry film, and the temperature curve and the flow of the reaction are shown in figure 1.

Example 5

Weighing 300g of polyether polyol (molecular weight: 2,000) subjected to vacuum drying and dehydration treatment and 52g of sodium bis-1,4- (2-hydroxyethoxy) -2-ethoxybutane sulfonate, uniformly stirring, heating to 60 ℃, weighing 71.1g of Toluene Diisocyanate (TDI), keeping the temperature at 95 ℃ for carrying out polymerization reaction for 2.5 hours, and reacting until the NCO content reaches a theoretical value to obtain a polyurethane prepolymer; the stirring rate was increased by adding 1320g of water directly dropwise to the polyurethane prepolymer, emulsifying for 10 minutes to convert the water phase, then adding 12.6g of hexamethylenediamine and 8.8g of phenylenediamine to obtain a sulfonic acid aqueous polyurethane emulsion, and adding 5 wt% (based on the total solid content of the emulsion) of a carbodiimide crosslinking agent before coating to improve the hydrolysis resistance of the dry film, wherein the temperature profile and the flow of the above reaction are shown in FIG. 1.

Product performance testing

i. Determination of the solid content

Weighing a dry watch glass, weighing the watch glass as m, weighing 1.5-2.0 g of the waterborne polyurethane emulsion, and flatly paving the waterborne polyurethane emulsion in the watch glass with the weight of m₀Drying at 120 deg.C for 2 hr, taking out, and weighing₁The solids content is calculated as follows:

solid content (%) = [ (m) ₁ -m)/m ₀ ] x100%。

Resistance to hydrolysis

The dry film was subjected to ISO 1419:1995 hydrolysis resistance test (Jungle test), humidity 95%, temperature 70 ℃ and test for retention of physical properties after leaving for one week.

Determination of emulsion stability

100g of the emulsion was stored at room temperature (25 ℃) and observed every other week for precipitation, the longer it took to precipitate, the better the stability.

TABLE 1 test results for the polyurethane emulsions of examples 1 to 5

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims

1. A sulfonic acid type aqueous polyurethane emulsion is characterized by comprising polyisocyanate, polyol, sulfonate functional polyether glycol type hydrophilic chain extender and solvent;

the sulfonate functional polyether glycol type hydrophilic chain extender comprises one or more of the following components: bis-1,4- (2-hydroxypropoxy) -2-propoxybutanesulfonate, potassium bis-1,4- (2-hydroxyethoxy) -2-ethoxybutanesulfonate, and sodium bis-1,4- (2-hydroxyethoxy) -2-ethoxybutanesulfonate.

2. The sulfonic acid type aqueous polyurethane emulsion according to claim 1, wherein the content of the sulfonic acid salt functional polyether glycol type hydrophilic chain extender is 1 to 35% by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion.

3. The sulfonic acid type aqueous polyurethane emulsion according to claim 1, wherein the polyisocyanate comprises a diisocyanate, the diisocyanate comprises one or more of toluene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, diphenylmethane 4, 4-diisocyanate, dicyclohexylmethane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, methylcyclohexyl diisocyanate and tetramethylxylylene diisocyanate.

4. The sulfonic acid type aqueous polyurethane emulsion according to claim 1, wherein the polyisocyanate is contained in an amount of 5 to 35% by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion.

5. The sulfonic acid type aqueous polyurethane emulsion according to claim 1, wherein the polyester polyol comprises one or more of polyester polyol, polylactone polyol, polyether polyol, polycarbonate polyol, polythioether polyol, mixed polymer polyol of polyether and polyester.

6. The sulfonic acid type aqueous polyurethane emulsion according to claim 1, wherein the content of the polymeric polyol is 45 to 80% by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion.

7. The sulfonic acid type waterborne polyurethane emulsion as claimed in claim 1, further comprising one or more of a catalyst, a small molecule chain extender, a hydrophilic chain extender and a cross-linking agent, wherein the catalyst comprises one or more of a tertiary amine catalyst, an organotin catalyst and a non-tin metal compound catalyst; the micromolecular chain extender comprises one or a combination of more of ethylenediamine, hexamethylenediamine, phenylenediamine, diethanolamine, polyoxypropylene triamine, diethylenetriamine, isophorone diamine, m-xylylenediamine and methyldiethanolamine; the hydrophilic chain extender comprises one or more of dimethylol propionic acid, dimethylol butyric acid, dihydroxy half ester, ethylene diamino ethanesulfonic acid sodium salt, diaminobenzene sulfonic acid sodium salt, diaminopropionic acid and diaminobutyric acid; the cross-linking agent comprises one or a combination of aliphatic isocyanate, polyethylenimine, a water-based epoxy cross-linking agent, a carbodiimide cross-linking agent and melamine-formaldehyde resin.

8. An adhesive film, which is characterized by being prepared from the sulfonic acid type aqueous polyurethane emulsion described in any one of claims 1 to 7.

9. A process for producing the sulfonic acid type aqueous polyurethane emulsion according to any one of claims 1 to 7, which comprises the steps of:

mixing the polyhydric alcohol and the sulfonate functional polyether glycol type hydrophilic chain extender to form a mixture;

adding a polyisocyanate to the mixture to produce a polyurethane prepolymer; and

adding a solvent into the polyurethane prepolymer, and emulsifying the polyurethane prepolymer to obtain the sulfonic acid type aqueous polyurethane emulsion.