阅读说明：本技术 一种填充用水性聚氨酯树脂及其制备方法 (Waterborne polyurethane resin for filling and preparation method thereof ) 是由 徐旭东 刘娅林 陈玉国 张留成 胡文翠 郭翠娟 耿俊玲 梁新新 于 2020-12-22 设计创作，主要内容包括：一种填充用水性聚氨酯树脂及其制备方法,一种填充用水性聚氨酯树脂,包括如下重量份数的物质：聚丙二醇500-600份,二异氰酸酯化合物120-180份,二羟甲基丁酸20-30份,催化剂0.1-0.3份,丙酮30-40份,扩链剂20-30份,中和剂10-18份,去离子水1200-1700份。本发明的产品发明的产品具有环保型、低毒性,产品低VOC等优点。填充后的皮革柔软度在2.5-3.0mm,合成革在4.0mm。本专利制备的填充用水性聚氨酯树脂在真皮厂和合成革厂应用后,可满足行业用革的要求。(The waterborne polyurethane resin for filling comprises the following components in parts by weight: 600 parts of polypropylene glycol, 180 parts of diisocyanate compound, 20-30 parts of dimethylolbutyric acid, 0.1-0.3 part of catalyst, 30-40 parts of acetone, 20-30 parts of chain extender, 10-18 parts of neutralizer and 1200 parts of deionized water. The product of the invention has the advantages of environmental protection, low toxicity, low VOC and the like. The softness of the filled leather is 2.5-3.0mm, and the softness of the synthetic leather is 4.0 mm. The waterborne polyurethane resin for filling prepared by the method can meet the requirements of industrial leather after being applied in a leather factory and a synthetic leather factory.)

1. A filling aqueous polyurethane resin characterized by comprising: the composition comprises the following substances in parts by weight:

600 parts of polypropylene glycol, 180 parts of diisocyanate compound, 20-30 parts of dimethylolbutyric acid, 0.1-0.3 part of catalyst, 30-40 parts of acetone, 20-30 parts of chain extender, 10-18 parts of neutralizer and 1200 parts of deionized water.

2. The aqueous filling polyurethane resin according to claim 1, wherein: the molecular weight of the polypropylene glycol is 2000.

3. The aqueous filling polyurethane resin according to claim 1, wherein: the diisocyanate compound is any one or two of hexamethylene diisocyanate and toluene diisocyanate which are mixed in any proportion.

4. The aqueous filling polyurethane resin according to claim 1, wherein: the catalyst is organic bismuth.

5. The aqueous filling polyurethane resin according to claim 1, wherein: the chain extender is any one or two of 1, 6-hexanediol, neopentyl glycol, piperazine and ethylenediamine which are mixed in any proportion.

6. The aqueous filling polyurethane resin according to claim 1, wherein: any one or two of the neutralizer N, N-dimethylethanolamine and triethylamine is mixed in any proportion.

7. The aqueous filling polyurethane resin according to claim 1, wherein: the application method of the aqueous polyurethane resin emulsion comprises the following steps: preparing an aqueous polyurethane resin emulsion: penetrant: leveling agent: medium shear thickening agent: and (2) weighing the low-shear thickening agent, namely wood powder, at a ratio of 1000:2:2:0.5:1:1, namely the aqueous polyurethane resin emulsion, the penetrating agent, the leveling agent, the high-shear thickening agent and the low-shear thickening agent, adding the penetrating agent and the leveling agent into the aqueous polyurethane resin emulsion, uniformly stirring by using a mechanical stirring device, adding the medium-shear thickening agent and the low-shear thickening agent, and continuously uniformly stirring by using the mechanical stirring device to complete the preparation of the waterborne polyurethane for filling.

8. The aqueous filling polyurethane resin according to claim 1, wherein:

the penetrating agent is medium 2440;

the leveling agent is 450 mm high;

the medium shear thickening agent is WH 601;

the low-shear thickening agent is WH 301;

the wood powder is 200-mesh wood powder.

9. A method for preparing a filling waterborne polyurethane resin is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: weighing polypropylene glycol by using an accurate weighing platform scale, transferring the polypropylene glycol into a dehydration reaction kettle, sealing and vacuumizing, dehydrating the polypropylene glycol for 1.5h under the conditions of negative pressure of-0.06 MPa and temperature of 120 ℃;

step two: transferring polypropylene glycol into a polymerization reaction kettle after dehydration is finished, cooling to below 60 ℃, accurately weighing diisocyanate compounds and catalysts, transferring the diisocyanate compounds and the catalysts into the polymerization reaction kettle, heating to 85 ℃, timing to perform preliminary polymerization reaction, and reacting for 1.5 h;

step three: after the primary polymerization reaction, carrying out cooling operation, after the temperature is reduced to below 55 ℃, adding an accurate amount of dimethylolbutyric acid and a catalyst into a polymerization reaction kettle, adding acetone to promote dissolution and reduce the viscosity of a polymer, heating to 75 ℃ to carry out graft polymerization reaction for 1.5h, and finishing the first step of graft polymerization reaction;

step four: and (3) cooling to 55 ℃ after the first-step graft polymerization reaction is finished, weighing an accurate amount of the front chain extender, adding the front chain extender into a polymerization reaction kettle, heating to 75 ℃ for graft polymerization reaction for 1.0h, and finishing the second-step graft polymerization reaction.

Step five: and cooling the prepolymer, transferring the prepolymer into an emulsifying kettle after the prepolymer is cooled to 55 ℃, and accurately metering by adopting the weighing scales of the reaction kettle. Determining the amount of a neutralizing agent added into an emulsifying kettle according to the weight and the neutralization degree, carrying out hydrophilic neutralization chain extension salifying reaction for 10min, adding deionized water, adding a rear chain extender after phase inversion is finished, and stirring and dispersing for 0.5 h;

step six: and after the reaction in the fifth step is finished, transferring the mixture in the emulsifying kettle to a distillation kettle, heating to 56-60 ℃, simultaneously starting a vacuum pump, heating and vacuumizing for 0.5h, and removing acetone to obtain the aqueous polyurethane resin emulsion.

Technical Field

The invention belongs to the field of leather spraying adhesives, and particularly relates to a waterborne polyurethane resin for filling and a preparation method thereof.

Background

After the original leather is treated by a leather tannery, the leather blank is divided into a first layer leather and a second layer leather, and the second layer leather is generally hard and has insufficient flexibility in the application process. For better utilization of the two-layered embryos, the embryos are usually filled with retanning fatliquoring, but this has limitations. With the increase of environmental protection pressure, the water field requirements of leather factories are more and more strict, and the improvement of the process is urgently needed. Similar problems are encountered when treating base fabrics in synthetic leather factories. The waterborne polyurethane resin for filling is researched in order to meet the environmental protection requirement and the market demand, and compared with a water field filler, the waterborne polyurethane resin for filling adopts water as a solvent, so that the environmental protection treatment pressure of a manufacturer is greatly reduced, the requirement of environmental protection is met, and the investment of water field equipment, sewage and the like can be reduced. The product of the invention has the advantages of environmental protection, low toxicity, low VOC and the like. The leather is suitable for improving the softness of the leather blank and the base cloth and simultaneously improving the hand feeling saturation of the leather blank and the base cloth. At present, the softness of leather is 2.5-3.0mm, and the softness of synthetic leather is 4.0 mm. Can completely meet the requirement of the market on softness.

Disclosure of Invention

The invention provides a filling waterborne polyurethane resin, which is used for overcoming the defects in the prior art.

The invention is realized by the following technical scheme:

the filling waterborne polyurethane resin comprises the following substances in parts by weight:

600 parts of polypropylene glycol, 180 parts of diisocyanate compound, 20-30 parts of dimethylolbutyric acid, 0.1-0.3 part of catalyst, 30-40 parts of acetone, 20-30 parts of chain extender, 10-18 parts of neutralizer and 1200 parts of deionized water.

The filling aqueous polyurethane resin as described above, wherein the molecular weight of the polypropylene glycol is 2000.

In the above-mentioned aqueous filling polyurethane resin, the diisocyanate compound is one or two of hexamethylene diisocyanate and toluene diisocyanate mixed at an arbitrary ratio.

The waterborne polyurethane resin for filling is characterized in that the catalyst is organic bismuth.

The filling waterborne polyurethane resin is characterized in that the chain extender is any one or two of 1, 6-hexanediol, neopentyl glycol, piperazine and ethylenediamine which are mixed in any proportion.

The filling aqueous polyurethane resin is characterized in that any one or two of the neutralizer N, N-dimethylethanolamine and triethylamine is mixed in any proportion.

The application method of the waterborne polyurethane resin emulsion for filling comprises the following steps: preparing an aqueous polyurethane resin emulsion: penetrant: leveling agent: medium shear thickening agent: and (2) weighing the low-shear thickening agent, namely wood powder, at a ratio of 1000:2:2:0.5:1:1, namely the aqueous polyurethane resin emulsion, the penetrating agent, the leveling agent, the high-shear thickening agent and the low-shear thickening agent, adding the penetrating agent and the leveling agent into the aqueous polyurethane resin emulsion, uniformly stirring by using a mechanical stirring device, adding the medium-shear thickening agent and the low-shear thickening agent, and continuously uniformly stirring by using the mechanical stirring device to complete the preparation of the waterborne polyurethane for filling.

The filling water-based polyurethane resin is the penetrating agent of 2440.

The filling waterborne polyurethane resin has the leveling agent with the height of 450.

The filling aqueous polyurethane resin is characterized in that the medium shear thickening agent is WH 601.

The filling water-based polyurethane resin is characterized in that the low-shear thickening agent is WH 301.

The filling waterborne polyurethane resin is wood powder of 200 meshes.

A preparation method of a filling waterborne polyurethane resin comprises the following steps:

the method comprises the following steps: weighing polypropylene glycol by using an accurate weighing platform scale, transferring the polypropylene glycol into a dehydration reaction kettle, sealing and vacuumizing, dehydrating the polypropylene glycol for 1.5h under the conditions of negative pressure of-0.06 MPa and temperature of 120 ℃;

step two: transferring polypropylene glycol into a polymerization reaction kettle after dehydration is finished, cooling to below 60 ℃, accurately weighing diisocyanate compounds and catalysts, transferring the diisocyanate compounds and the catalysts into the polymerization reaction kettle, heating to 85 ℃, timing to perform preliminary polymerization reaction, and reacting for 1.5 h;

step three: after the primary polymerization reaction, carrying out cooling operation, after the temperature is reduced to below 55 ℃, adding an accurate amount of dimethylolbutyric acid and a catalyst into a polymerization reaction kettle, adding acetone to promote dissolution and reduce the viscosity of a polymer, heating to 75 ℃ to carry out graft polymerization reaction for 1.5h, and finishing the first step of graft polymerization reaction;

step four: and (3) cooling to 55 ℃ after the first-step graft polymerization reaction is finished, weighing an accurate amount of the front chain extender, adding the front chain extender into a polymerization reaction kettle, heating to 75 ℃ for graft polymerization reaction for 1.0h, and finishing the second-step graft polymerization reaction.

Step five: and cooling the prepolymer, transferring the prepolymer into an emulsifying kettle after the prepolymer is cooled to 55 ℃, and accurately metering by adopting the weighing scales of the reaction kettle. Determining the amount of a neutralizing agent added into an emulsifying kettle according to the weight and the neutralization degree, carrying out hydrophilic neutralization chain extension salifying reaction for 10min, adding deionized water, adding a rear chain extender after phase inversion is finished, and stirring and dispersing for 0.5 h;

step six: and after the reaction in the fifth step is finished, transferring the mixture in the emulsifying kettle to a distillation kettle, heating to 56-60 ℃, simultaneously starting a vacuum pump, heating and vacuumizing for 0.5h, and removing acetone to obtain the aqueous polyurethane resin emulsion.

The invention has the advantages that:

1. the product of the invention has the advantages of environmental protection, low toxicity, low VOC and the like. The softness of the filled leather is 2.5-3.0mm, and the softness of the synthetic leather is 4.0 mm. The waterborne polyurethane resin for filling prepared by the method can meet the requirements of industrial leather after being applied in a leather factory and a synthetic leather factory.

2. The filling material is used in the market, a rotary drum production process is generally used, the production cost, the equipment input cost and the subsequent wastewater treatment cost are greatly increased, the filling process adopted by the invention can reduce the cost in all aspects and simplify the production process, and the external popularization of the product is facilitated.

3. The requirement for VOC measurement is higher and higher in the existing production field of genuine leather and synthetic leather, the demand of the product for acetone is very small, the acetone is basically eliminated completely when acetone is removed in the later period, the measurement requirement of VOC of each industrial standard can be met, in addition, no adverse effect is caused to operators during production and field application, the product is easy to store safely, no potential risk is caused, and the obvious environment-friendly advantage is achieved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a schematic diagram showing the results of detection in example 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The method comprises the following steps: accurately weighing 576kg of polypropylene glycol by a reduction method, transferring the polypropylene glycol into a dehydration reaction kettle, sealing, vacuumizing, dehydrating the polypropylene glycol for 1.5h under the conditions of negative pressure of-0.06 MPa and temperature of 120 ℃;

step two: transferring polypropylene glycol into a polymerization reaction kettle after dehydration is finished, cooling to below 60 ℃, weighing 140kg of toluene diisocyanate and 0.18kg of organic bismuth, adding the toluene diisocyanate and the organic bismuth into the polymerization reaction kettle, heating to 85 ℃, timing to start preliminary prepolymerization reaction, and reacting for 1.5 h;

step three: after the reaction is finished, cooling to 55 ℃, adding 23.5kg of dimethylolbutyric acid and 40kg of acetone into a prepolymerization reaction kettle, heating to 75 ℃ to perform graft polymerization pre-reaction for 1.5h, and finishing the first step of graft polymerization reaction;

step four: and (3) after the first-step graft polymerization reaction is finished, cooling to 55 ℃, adding 9kg of neopentyl glycol serving as a front chain extender, heating to 75 ℃ for graft polymerization reaction for 1 hour, and finishing the second-step reaction.

Step five: cooling the prepolymer, transferring the prepolymer into an emulsifying kettle after the temperature is reduced to 55 ℃, adding 14kg of N, N-dimethylethanolamine into the emulsifying kettle, carrying out the hydrophilic neutralization chain extension salifying reaction in the third step, reacting for 10min, adding 1350kg of deionized water, adding 4kg of rear chain extender ethylenediamine after the phase inversion is finished, and continuously stirring and reacting for 0.5 h;

step six: and after the reaction in the fifth step is finished, transferring the mixture in the emulsifying kettle to a distillation kettle, heating to 56-60 ℃, simultaneously starting a vacuum pump, heating and vacuumizing for 0.5h, and removing acetone to obtain the waterborne polyurethane resin emulsion with the solid content of 35%. Detecting the film forming performance of the emulsion, wherein the film hardness is 15 Shore A; the tensile strength of the film is 1.8MPa, and the elongation at break of the film is 750%.

The application method of the aqueous polyurethane resin emulsion comprises the following steps: preparing an aqueous polyurethane resin emulsion: penetrant: leveling agent: medium shear thickening agent: and (2) weighing the low-shear thickening agent, namely wood powder, at a ratio of 1000:2:2:0.5:1:1, adding the penetrating agent and the leveling agent into the aqueous polyurethane resin emulsion, uniformly stirring by using a mechanical stirring device, adding the medium-shear thickening agent and the low-shear thickening agent, and continuously uniformly stirring by using the mechanical stirring device to complete the preparation of the aqueous polyurethane for filling.

Product inspection report:

the leather blank is filled by adopting a three-plate printing mode, the filling material loading amount is controlled to be 10 threads, the physical property detection is carried out after the leather blank is dried, the softness is 2.6mm, and the requirement of a manufacturer on the production of the leather blank is met.

Example 2

A preparation method of waterborne polyurethane for filling comprises the following steps:

the method comprises the following steps: accurately weighing 500kg of polypropylene glycol by adopting a reduction method, transferring the polypropylene glycol into a dehydration reaction kettle, sealing, vacuumizing, dehydrating the polypropylene glycol for 1.5h under the conditions of negative pressure of-0.06 MPa and temperature of 120 ℃;

step two: transferring polypropylene glycol into a polymerization reaction kettle after dehydration is finished, cooling to below 60 ℃, weighing 120kg of toluene diisocyanate and 10kg of hexamethylene diisocyanate, transferring the toluene diisocyanate and the hexamethylene diisocyanate into the polymerization reaction kettle, heating to 85 ℃, timing to perform a first-step prepolymerization reaction, and reacting for 1.5 h;

step three: after the reaction is finished, cooling to 55 ℃, adding 20kg of dimethylolbutyric acid and 30kg of acetone into a prepolymerization reaction kettle, heating to 75 ℃ to carry out graft polymerization pre-reaction for 1.5h, and finishing the first-step graft polymerization reaction;

step four: and (3) after the first-step graft polymerization reaction is finished, cooling to 55 ℃, adding 20kg of front chain extender 1.6 hexanediol, heating to 75 ℃ for polymerization reaction for 1h, and finishing the second-step reaction.

Step five: cooling the prepolymer, transferring the prepolymer into an emulsifying kettle after the temperature is reduced to 55 ℃, adding 13kg of triethylamine into the emulsifying kettle, carrying out the third step of hydrophilic neutralization chain extension salifying reaction for 0.5h, adding 1200kg of deionized water, adding 2kg of rear chain extender ethylenediamine after the phase inversion is finished, and continuously stirring for reaction for 0.5 h;

step six: and after the reaction in the fifth step is finished, transferring the mixture in the emulsifying kettle to a distillation kettle, heating to 56-60 ℃, simultaneously starting a vacuum pump, heating and vacuumizing for 0.5h, and removing acetone to obtain the waterborne polyurethane resin emulsion with the solid content of 34%. Detecting the film forming property of the emulsion, wherein the film hardness is 10 Shore A; the tensile strength of the film is 1.4MPa, and the elongation at break of the film is 800%.

The application method of the aqueous polyurethane resin emulsion comprises the following steps: preparing an aqueous polyurethane resin emulsion: penetrant: leveling agent: medium shear thickening agent: the low shear thickening agent is 1000:2:2:0.5: the preparation method comprises the following steps of 1, weighing the aqueous polyurethane resin emulsion, the penetrating agent, the leveling agent, the medium-shear thickening agent and the low-shear thickening agent according to a proportion, adding the penetrating agent and the leveling agent into the aqueous polyurethane resin emulsion, uniformly stirring by using a mechanical stirring device, adding the medium-shear thickening agent and the low-shear thickening agent, and continuously uniformly stirring by using the mechanical stirring device to complete the preparation of the aqueous polyurethane for filling.

And (3) performance detection:

and (3) filling the synthetic leather base cloth by adopting a three-plate printing mode, controlling the filling material loading amount to be 15 threads, detecting the physical property after drying, and meeting the requirement of a manufacturer on base cloth production, wherein the softness is 3.9 mm.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.