CN109575220B - Quick-rebound aqueous polyurethane urea elastomer and preparation method thereof - Google Patents
Quick-rebound aqueous polyurethane urea elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a quick-rebound aqueous polyurethane-urea elastomer and a preparation method thereof. According to the invention, ether-based macromolecular diamine reacts with isocyanate to generate urea bonds, so that physical crosslinking provided by hydrogen bonds is formed among molecular chains, and chemical crosslinking among the molecular chains is generated by reaction of ketone-containing carbonyl and hydrazine; the synergistic effect of hydrogen bond physical crosslinking and ketone hydrazine chemical crosslinking imitates a rubber structure, and has high strength and quick rebound performance.
Description
Technical Field
The invention relates to synthesis of aqueous polyurethane urea emulsion and preparation of aqueous polyurethane urea elastomer, belonging to the field of high polymer materials.
Background
The waterborne polyurethane is a novel polyurethane system which takes water as a medium to replace an organic solvent. The waterborne polyurethane has the advantages of nonflammability, no toxicity, adjustable viscosity fluidity and easy processing, has the performances of high wear resistance, tearing resistance and good cohesiveness with solvent type polyurethane, and is widely applied to coatings, adhesives and elastomers. The polyurethane applied to the elastomer is a high-molecular synthetic material with the performance between that of rubber and plastic, and compared with rubber, the polyurethane is characterized in that the molecular structure of the polyurethane does not contain unsaturated chemical bonds, so that the polyurethane has excellent aging resistance and long service life. And thirdly, the processing and molding process of the polyurethane is simple, the polyurethane can be molded by one-time injection molding or one-time casting, and the room-temperature curing of the polyurethane can be realized by the change of the type and the content of the catalyst. However, compared with rubber elastomers, common aqueous polyurethane elastomers have poor resilience, because the rubber elastomers have a large number of chemical crosslinking points due to the vulcanization process in the forming process, the molecular weight between the crosslinking points is usually large, and the common polyurethane elastomers have only a small number of weak physical crosslinking points provided by hydrogen bonds.
Disclosure of Invention
The invention aims to provide a waterborne polyurethane-urea elastomer and a preparation method thereof, which overcome the defect that the strength and resilience of the existing waterborne polyurethane elastomer cannot coexist, introduce a carbamido structure to provide a physical crosslinking point and ensure a proper chemical crosslinking structure.
The technical purpose of the invention is realized by the following technical scheme:
the preparation method of the waterborne polyurethane-urea elastomer comprises the following steps:
step 1, carrying out vacuum pumping treatment on polyhydric alcohol and ether-based macromolecular diamine at 90-120 ℃ to completely dehydrate and avoid the influence of water on the reaction;
in the step 1, the polyhydric alcohol and the ether-based macromolecular diamine are vacuumized for 1-2 hours at the temperature of 90-120 ℃.
In step 1, the polyhydric alcohol and the ether-based macrodiamine are placed in a high-temperature warehouse at the temperature of 100-120 ℃ for 2-5 days before being vacuumized, wherein the time is 24 hours each day.
Step 2, naturally cooling the polyol and the ether-based macromolecular diamine subjected to the vacuum pumping treatment in the step 1 to 50-55 ℃, adding a solvent, diisocyanate, a first cross-linking agent, a hydrophilic chain extender and a catalyst into a reaction kettle by adopting a one-step feeding method, uniformly mixing, and then heating to 60-90 ℃ for reaction;
in step 2, the reaction temperature is 70 to 80 ℃ and the reaction time is 2 to 10 hours, preferably 5 to 8 hours.
Step 3, naturally cooling to 50-55 ℃ after the reaction in the step 2, adding a solvent to reduce the viscosity of the system to be less than 10000mP.s, naturally cooling to 20-30 ℃, adding a neutralizer to react, naturally cooling to 5-10 ℃, adding water to stir at a high speed for emulsification, and forming a polyurethane urea emulsion;
in the step 3, adding a neutralizing agent to react for 10-30 min; the high-speed stirring speed is 1000-2000 revolutions per minute, and the emulsifying time is 10-30 min.
In step 3, adding a solvent to reduce the viscosity of the reaction system, wherein the adding amount of the solvent is determined according to the viscosity test result of the reaction system. The type of the solvent added in the step 3 is the same as that of the solvent added in the step 2.
And 4, adding a second cross-linking agent into the polyurethane urea emulsion prepared in the step 3 for reaction, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed.
In the step 4, a second cross-linking agent is added for reaction, the high-speed stirring speed is kept at 1000-2000 revolutions per minute, and the reaction time is 10-30 min.
When the polyurethane urea emulsion prepared by the method is used, the forming treatment is carried out according to the prior art requirements, such as dipping forming, film laying forming, rotary forming, coating forming or coating forming, and the polyurethane urea elastomer can be obtained after the water phase (moisture) in the emulsion is evaporated.
In the preparation method, the raw material components are as follows in parts by mass: 15-30 parts of polyol, 1-10 parts of ether-based macromolecular diamine, 10-30 parts of a solvent used in the step 2, 10-30 parts of diisocyanate, 1-10 parts of a first cross-linking agent, 3-8 parts of a hydrophilic chain extender, 0.1-0.3 part of a catalyst, 1-6 parts of a neutralizing agent, 30-50 parts of water and 1-5 parts of a second cross-linking agent.
In the preparation method, the raw material components are preferably selected from the following components in parts by mass: 20-30 parts of polyol, 5-10 parts of ether-based macromolecular diamine, 20-30 parts of a solvent used in the step 2, 15-25 parts of diisocyanate, 3-8 parts of a first cross-linking agent, 5-8 parts of a hydrophilic chain extender, 0.1-0.3 part of a catalyst, 1-5 parts of a neutralizing agent, 40-50 parts of water and 2-5 parts of a second cross-linking agent.
The polyhydric alcohol has a plurality of hydroxyl groups and is selected from poly adipic acid-1, 4-butanediol ester dihydric alcohol, polytetrahydrofuran ether dihydric alcohol or polyoxypropylene dihydric alcohol.
The number average molecular weight of the polyethylene oxide or polypropylene oxide with the end group of the ether-based macromolecular diamine being amino is 200-4000, preferably 1000-3000.
The solvent is selected from organic solvent selected from acetone, dioxane or N, N-dimethylacetamide.
The diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate.
The first cross-linking agent is a reaction monomer containing ketone carbonyl and active hydrogen, and N- [ (1, 1-dimethyl-2-acetyl) ethyl ] -beta-dihydroxyethylamino propionamide, N' -diacetone propionamido ethylenediamine or 5- [ bis (2-hydroxyethyl) amino ] -2-pentanone is selected.
The hydrophilic chain extender is hydroxyl-containing carboxylic acid and is selected from dimethylolpropionic acid or dimethylolbutyric acid.
The catalyst is organic tin catalyst selected from dibutyl tin dilaurate or stannous octoate.
The neutralizing agent is selected from triethylamine, sodium hydroxide or potassium hydroxide.
The second crosslinking agent is selected from carbonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, succinic acid dihydrazide or isophthalic acid dihydrazide.
The aqueous polyurethane elastomer emulsion (namely the aqueous emulsion with the uniformly dispersed polyurethane urea elastomer) prepared by the invention can stably exist for more than 12 months, a TDZ5-WS centrifuge is adopted to carry out centrifugal treatment at the rotating speed of 3000 r/min, and no precipitate is generated after centrifugal rotation for 30 min; with Multisizer 4e KualThe special particle size analyzer analyzes the particle size of the emulsion, and the particle size of the emulsion is between 0.01 and 0.6 microns. The polyurethaneurea elastomers prepared in accordance with the present invention were tested by infrared spectroscopy (i.e., rotational molding of the polyurethaneurea elastomer after removal of water) as shown in FIG. 1, 3324.71cm-1Is the stretching vibration peak of the residual hydroxyl group, 2961.07cm-1And 2904.57cm-1Respectively is the stretching vibration peak of C-H on the methyl methylene, and the stretching vibration peak of the carbonyl group in the carbamate group is reported to be distributed at 1730-1760cm-1In the range, the stretching vibration peak of carbonyl in the carbamido is distributed at 1680-1715cm-1Within the range. The stretching vibration peak of carbonyl in FIG. 1 appears at 1689.54cm-1It is stated that there is the formation of urea groups in the polymer and hydrogen bonding. At 1303.37cm-1The absorption peak is the vibration peak of C-O-C in the ethylene oxide chain, and the red shift occurs after the chain extension, which indicates that the hydrogen bond action occurs between polymer molecules. Infrared spectroscopic analysis shows that the monomers undergo polymerization reactions according to the expected route to form the polyurethaneurea structure.
The aqueous polyurethane urea elastomer emulsion prepared by the invention is subjected to spin coating forming, the polyurethane urea elastomer can be obtained after water in the emulsion is evaporated, and the mechanical property test is carried out according to GBT 528-2009, wherein the tensile strength of the elastomer is 15-35 MPa, the elongation at break is 200-1000%, and the breaking strength is 1-3 MPa. Compared with the prior art, the ether-based macromolecular diamine and isocyanate react to generate urea bonds, so that physical crosslinking provided by hydrogen bonds is formed among molecular chains, hydrazine and ketone-containing carbonyl are added after water is added for emulsification and dispersion to generate chemical crosslinking among the molecular chains, and an emulsion structure is not damaged; the synergistic effect of hydrogen bond physical crosslinking and ketone hydrazine chemical crosslinking imitates a rubber structure, and has high strength and quick rebound performance.
The waterborne polyurethane urea elastomer emulsion is used as a film forming substance, and is blended with rubber powder, a film forming additive and a pigment filler to form a waterborne polyurethane track material, wherein the film forming substance is 30-60 parts by mass, the rubber powder is 30-60 parts by mass, the film forming additive is 1-10 parts by mass, the pigment filler is 10-30 parts by mass, preferably the film forming substance is 40-60 parts by mass, the rubber powder is 30-50 parts by mass, the film forming additive is 5-10 parts by mass, and the pigment filler is 10-20 parts by mass.
The rubber powder has a particle size distribution within the range of 0.1-2 mm, and is selected from natural rubber powder, styrene-butadiene rubber powder, chloroprene rubber powder, ethylene propylene diene monomer rubber powder, thermoplastic styrene elastomer rubber powder or polyurethane thermoplastic elastomer rubber powder.
The pigment and filler is selected from talcum powder, calcium carbonate, white carbon black, diatomite, kaolin or heavy calcium carbonate, and powdery material with the grain diameter of 200-500 meshes.
The film-forming assistant consists of 1-10 parts by mass of a water-based wetting dispersant, a defoaming agent, a thickening agent, a delustering agent and a pH regulator (the film-forming assistant is 1-10 parts by mass), wherein 1-6 parts by mass of the water-based wetting dispersant, 0.1-0.5 part by mass of the defoaming agent, 1-3 parts by mass of the thickening agent, 0.1-0.5 part by mass of the delustering agent and 0.1-0.5 part by mass of the pH regulator.
The mechanical property test is carried out according to GBT 528-. Constructing a runway by using the runway material and the waterborne polyurethane-urea elastomer, wherein the runway consists of an elastic layer and an anti-skid layer arranged on the elastic layer, the thickness of the elastic layer is 6-10 mm, and the thickness of the anti-skid layer is 1-2 mm; the elastic layer is formed by a track material, is arranged on the elastic layer by adopting aqueous polyurethane urea elastomer emulsion (spraying, brushing, coating or dipping), and forms an anti-skid layer after being formed.
Compared with the prior art, the waterborne polyurethane track material applied to the sports ground has better rebound resilience and mechanical strength, the drying time meets the construction requirement, meanwhile, the formula and the process are green and environment-friendly, and the raw materials can adopt commercially available raw materials, so that the use and the preparation are convenient.
Drawings
FIG. 1 is an infrared spectrum of a polyurethaneurea prepared according to the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention. The polyhydric alcohol and ether-based macrodiamine used in the examples were placed in a high-temperature 100-120 ℃ storage for 2-5 days, 24 hours per day, before being evacuated. The raw materials are mostly purchased from direct markets, such as Yangzhou Hengsheng chemical Co., Ltd, Tianjin Kowa chemical reagent Co., Ltd.
Example 1
Step 1, carrying out vacuum pumping treatment on polyoxypropylene diol-1000 (number average molecular weight 1000) and polypropylene oxide-1000 (number average molecular weight 1000) with an amino group as a terminal group at 120 ℃ for 1h to completely dehydrate;
step 2, naturally cooling the polyoxypropylene diol-1000 (with the number average molecular weight of 1000) and the polypropylene oxide-1000 subjected to the vacuum-pumping treatment in the step 1 to 55 ℃, adding acetone, isophorone diisocyanate, a first cross-linking agent N- [ (1, 1-dimethyl-2-acetyl) ethyl ] -beta-dihydroxyethylamino propionamide, a hydrophilic chain extender dimethylolpropionic acid and a catalyst dibutyl tin dilaurate into a reaction kettle, uniformly mixing, and heating to 90 ℃ for reaction for 2 hours, wherein 30g of polyol, 10g of ether-based macromolecular diamine, 20g of solvent, 30g of isophorone diisocyanate, 10g of first cross-linking agent, 8g of hydrophilic chain extender and 0.3g of catalyst are adopted;
step 3, after the reaction in the step 2 is finished, naturally cooling to 55 ℃, adding acetone serving as a solvent to reduce the viscosity of the system to 10000mP.s, naturally cooling to 30 ℃, adding 6g of triethylamine serving as a neutralizing agent to react for 30min, naturally cooling to 5 ℃, adding water to stir and emulsify at a high speed, wherein the stirring speed is 1500 revolutions per minute, and the emulsifying time is 30min to form a polyurethane urea emulsion;
and 4, adding 5g of a second cross-linking agent adipic dihydrazide into the polyurethane urea emulsion prepared in the step 3 for reaction for 30min, keeping the stirring speed at 1500 rpm, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed.
And (3) spreading the obtained polyurethane urea emulsion on a film, and standing at the room temperature of 20-25 ℃ for 1 day (namely 24 hours) to form to obtain the polyurethane urea elastomer.
Example 2
Step 1, carrying out vacuum pumping treatment on polytetrahydrofuran ether dihydric alcohol-600 (number average molecular weight 600) and polyethylene oxide-2000 (number average molecular weight 2000) with an amino group as a terminal group at 90 ℃ for 2h to completely dehydrate;
step 2, naturally cooling the polytetrahydrofuran ether diol-600 (with the number average molecular weight of 600) subjected to vacuum pumping treatment in the step 1 and the polyethylene oxide-2000 (with the number average molecular weight of 2000) with the end group being amino to 50 ℃, adding a solvent dioxane, hexamethylene diisocyanate, a first cross-linking agent 5- [ bis (2-hydroxyethyl) amino ] -2-pentanone, a hydrophilic chain extender dimethylolbutyric acid and a catalyst dibutyl tin dilaurate into a reaction kettle, uniformly mixing, and heating to 60 ℃ for reaction for 10 hours, wherein 15g of polyol, 1g of ether-based macromolecular diamine, 10g of solvent, 10g of hexamethylene diisocyanate, 1g of first cross-linking agent, 3g of hydrophilic chain extender and 0.1g of catalyst are added;
step 3, naturally cooling to 50 ℃ after the reaction in the step 2, adding a solvent dioxane to reduce the viscosity of the system to 8000mP.s, naturally cooling to 20 ℃, adding 1g of a neutralizing agent sodium hydroxide to react for 10min, naturally cooling to 8 ℃, adding water to stir at a high speed for emulsification, wherein the stirring speed is 2000 revolutions per minute, and the emulsification time is 10min, so as to form a polyurethane urea emulsion;
and 4, adding 1g of second cross-linking agent carbodihydrazide into the polyurethane urea emulsion prepared in the step 3 for reaction for 10min, keeping the stirring speed at 2000 revolutions per minute, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed.
And (3) spreading the obtained polyurethane urea emulsion on a film, and standing at the room temperature of 20-25 ℃ for 1 day (namely 24 hours) to form to obtain the polyurethane urea elastomer.
Example 3
Step 1, carrying out vacuum pumping treatment on poly adipic acid-1, 4-butanediol ester dihydric alcohol (with the number average molecular weight of 1000) and poly propylene oxide-2000 (with the number average molecular weight of 2000) with an amino group as an end group at 100 ℃ for 1.5h to completely dehydrate;
step 2, naturally cooling the poly (1, 4-butylene glycol) diol (with the number average molecular weight of 1000) and the poly (propylene oxide) -1000 (with the number average molecular weight of 1000) subjected to the vacuum-pumping treatment in the step 1 to 52 ℃, adding a solvent N, N-dimethylacetamide, isophorone diisocyanate, a first cross-linking agent N, N' -diacetone propionamidoethylenediamine, a hydrophilic chain extender dimethylolpropionic acid and a catalyst stannous octoate into a reaction kettle, uniformly mixing, and heating to 80 ℃ for reaction for 5 hours, wherein 20g of polyol, 5g of ether-based macromolecular diamine, 30g of solvent, 25g of isophorone diisocyanate, 8g of first cross-linking agent, 5g of hydrophilic chain extender and 0.2g of catalyst are added;
step 3, after the reaction in the step 2 is finished, naturally cooling to 55 ℃, adding a solvent acetone to reduce the viscosity of the system to 7500mP.s, naturally cooling to 25 ℃, adding 5g of a neutralizing agent potassium hydroxide to react for 20min, then naturally cooling to 10 ℃, adding water to stir and emulsify at a high speed, wherein the stirring speed is 2000 revolutions per minute, and the emulsifying time is 20min, so as to form a polyurethane urea emulsion;
and 4, adding 3g of a second cross-linking agent, namely sebacic dihydrazide, into the polyurethane urea emulsion prepared in the step 3, reacting for 20min, keeping the stirring speed at 1000 revolutions per minute, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water-phase emulsion in which the polyurethane urea elastomer is uniformly dispersed.
And (3) spreading the obtained polyurethane urea emulsion on a film, and standing at the room temperature of 20-25 ℃ for 1 day (namely 24 hours) to form to obtain the polyurethane urea elastomer.
Example 4
Step 1, carrying out vacuum pumping treatment on polyoxypropylene diol-4000 (number average molecular weight 4000) and amino-terminated polypropylene oxide-4000 (number average molecular weight 4000) at 100 ℃ for 1h to completely dehydrate;
step 2, naturally cooling the polyoxypropylene diol-4000 (with the number average molecular weight of 4000) subjected to the vacuum-pumping treatment in the step 1 and the polypropylene oxide-4000 (with the number average molecular weight of 4000) with an amino group as an end group to 50 ℃, adding a solvent N, N-dimethylacetamide, isophorone diisocyanate, a first cross-linking agent N, N' -diacetone propionamidoethylenediamine, a hydrophilic chain extender dimethylolbutyric acid and a catalyst stannous octoate into a reaction kettle, uniformly mixing, and heating to 90 ℃ for 5 hours for reaction, wherein the polyol is 20g, the ether-based macromolecular diamine is 10g, the solvent is 20g, the isophorone diisocyanate is 15g, the first cross-linking agent is 3g, the hydrophilic chain extender is 5g, and the catalyst is 0.1 g;
step 3, after the reaction in the step 2 is finished, naturally cooling to 52 ℃, adding a solvent N, N-dimethylacetamide to reduce the viscosity of the system to 9000mP.s, naturally cooling to 25 ℃, adding 3g of triethylamine serving as a neutralizing agent to react for 30min, naturally cooling to 5 ℃, adding water to stir at a high speed for emulsification at a stirring speed of 1500 revolutions per minute for 25min, and forming a polyurethane urea emulsion;
and 4, adding 5g of second cross-linking agent carbodihydrazide into the polyurethane urea emulsion prepared in the step 3 for reaction for 15min, keeping the stirring speed at 1500 rpm, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed.
And (3) spreading the obtained polyurethane urea emulsion on a film, and standing at the room temperature of 20-25 ℃ for 1 day (namely 24 hours) to form to obtain the polyurethane urea elastomer.
Example 5
Step 1, carrying out vacuum pumping treatment on polyoxypropylene diol-600 (number average molecular weight 600) and amino-terminated polypropylene oxide-200 (number average molecular weight 200) at 90 ℃ for 1h to completely dehydrate;
step 2, naturally cooling the polyoxypropylene diol-600 (with the number average molecular weight of 600) subjected to the vacuum-pumping treatment in the step 1 and the polypropylene oxide-200 (with the number average molecular weight of 200) with the amino group as the end group to 50 ℃, adding a solvent N, N-dimethylacetamide, hexamethylene diisocyanate, a first cross-linking agent N, N' -diacetone propionamidoethylenediamine, a hydrophilic chain extender dimethylolpropionic acid and a catalyst dibutyl tin dilaurate into a reaction kettle, uniformly mixing, and heating to 70 ℃ to react for 8 hours, wherein 30g of polyol, 5g of ether-based macromolecular diamine, 25g of the solvent, 15g of hexamethylene diisocyanate, 3g of the first cross-linking agent, 5g of the hydrophilic chain extender and 0.3g of the catalyst are added;
step 3, after the reaction in the step 2 is finished, naturally cooling to 50 ℃, adding a solvent N, N-dimethylacetamide to reduce the viscosity of the system to 7000mP.s, naturally cooling to 20 ℃, adding 2g of triethylamine serving as a neutralizing agent to react for 15min, naturally cooling to 5 ℃, adding water to stir at a high speed for emulsification at a stirring speed of 2000 revolutions per minute for 15min, and forming a polyurethane urea emulsion;
and 4, adding 2g of second cross-linking agent succinic dihydrazide into the polyurethane urea emulsion prepared in the step 3 for reaction for 30min, keeping the stirring speed at 2000 revolutions per minute, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed.
And (3) spreading the obtained polyurethane urea emulsion on a film, and standing at the room temperature of 20-25 ℃ for 1 day (namely 24 hours) to form to obtain the polyurethane urea elastomer.
The mechanical property test of the polyurethane urea elastomer prepared in the above examples 1-5 is performed according to GBT 528-.
The aqueous phase emulsion with the uniformly dispersed polyurethane urea elastomer prepared in the above examples 1 to 5 is used as a film forming substance, the rubber powder, the film forming additive and the pigment filler are blended to form the aqueous polyurethane track material, the mechanical stirring is adopted for 300 to 500 revolutions per minute to realize uniform dispersion, the thickening agent is added into the aqueous polyurethane urea emulsion, the stirring is uniform, the aqueous wetting dispersant, the delustering agent, the pH value regulator and the defoaming agent are added, and the dispersion is uniform; adding pigment and filler, and stirring uniformly; adding rubber powder, and stirring uniformly; filtering and packaging. When in construction application, the runway material can be directly sprayed and constructed, and the formula of the runway material is as follows:
example 1 of runway Material formulation
60g of aqueous emulsion prepared in example 1 and uniformly dispersed with a polyurethane urea elastomer, 30g of 500-mesh calcium carbonate, 60g of 200-mesh styrene-butadiene rubber powder and 10g of a film-forming aid, wherein: 6g of an aqueous wetting dispersant BYK-154, 3g of a thickener PVC, 0.2g of a matting agent (model: MH828), 0.5g of a 0.5gpH regulator (model: AMP-95), 0.3g of an antifoaming agent (model: SD 998).
Example 2 of runway Material formulation
30g of the aqueous phase emulsion uniformly dispersed with the polyurethane urea elastomer prepared in example 2, 10g of 500-mesh white carbon black, 30g of 200-mesh chloroprene rubber powder and 8g of a film-forming assistant, wherein: 4g of an aqueous wetting dispersant BYK-154, 2.5g of a thickener PVC, 0.5g of a matting agent (model: MH828), 0.5g of a 0.5gpH regulator (model: AMP-95), 0.5g of an antifoam agent (model: SD 998).
Example 3 of runway Material formulation
40g of the aqueous emulsion prepared in example 3 in which the polyurethane urea elastomer was uniformly dispersed, 20g of 200-mesh diatomaceous earth, 40g of 200-mesh natural rubber powder, and 5g of a film-forming aid, wherein: 2g of an aqueous wetting dispersant BYK-154, 1.5g of a thickener PVC, 0.5g of a matting agent (model: MH828), 0.5g of a 0.5gpH regulator (model: AMP-95), 0.5g of an antifoaming agent (model: SD 998).
Example 4 of runway Material formulation
50g of the aqueous phase emulsion prepared in example 4 and uniformly dispersed with the polyurethane urea elastomer, 15g of kaolin with 300 meshes, 30g of chloroprene rubber powder with 200 meshes and 6g of film-forming additive, wherein: 4g of an aqueous wetting dispersant BYK-154, 1g of a thickener PVC, 0.5g of a matting agent (model: MH828), 0.3gpH regulator (model: AMP-95), 0.2g of an antifoaming agent (model: SD 998).
Example 5 of runway Material formulation
50g of aqueous phase emulsion prepared in example 5 and uniformly dispersed with a polyurethane urea elastomer, 20g of 300-mesh talcum powder, 50g of 200-mesh ethylene propylene diene monomer rubber powder and a film-forming additive 5, wherein: 2g of an aqueous wetting dispersant BYK-154, 2g of a thickener PVC, 0.2g of a matting agent (model: MH828), 0.3gpH regulator (model: AMP-95), 0.5g of an antifoaming agent (model: SD 998).
The mechanical property test of the runway material prepared in the embodiment 1-5 of the runway material formula is carried out according to GBT 528-adulterated 2009, the breaking strength of the runway material is 0.6 MPa-1.5 MPa, and the elongation at break is 60-200%.
Constructing a runway by using the runway material and the waterborne polyurethane-urea elastomer, wherein the runway consists of an elastic layer and an anti-skid layer arranged on the elastic layer, the thickness of the elastic layer is 6mm, and the thickness of the anti-skid layer is 2 mm; the elastic layer is formed by a track material, is arranged on the elastic layer by adopting aqueous polyurethane urea elastomer emulsion (spraying, brushing, coating or dipping), and forms an anti-skid layer after being formed. Surface drying time (23 +/-2 ℃) for 1 hour, wherein the thickness of the coating is 2 mm; run-dry time (23. + -.2 ℃ C.: 2mm thick coating, 48h, test after track construction as shown in the following table:
| item | Index (I) | Results |
| Shock absorption | 35～50 | 45 |
| Tensile strength | ≥0.5 | 1.5MPa |
| Elongation at Break | ≥40 | 200％ |
| Rate of compression recovery | ≥90％ | 98％ |
| Flame retardant grade | I | I |
In addition, the method can intuitively feel that the product prepared by the invention is not pungent and basically tasteless, so that the invention has lower VOC emission and shows better environmental protection performance.
The preparation process is adjusted according to the content of the invention, the preparation of the waterborne polyurethane-urea elastomer emulsion, the polyurethane-urea elastomer and the runway material can be realized, and basically consistent performance is shown. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (13)
1. An aqueous polyurethane urea elastomer, characterized by being prepared according to the following steps:
step 1, carrying out vacuum pumping treatment on polyhydric alcohol and ether-based macromolecular diamine at 90-120 ℃ to completely dehydrate and avoid the influence of water on the reaction; the polyalcohol is selected from poly adipic acid-1, 4-butanediol diol ester diol, polytetrahydrofuran ether diol or polypropylene oxide diol; the ether-based macromolecular diamine is polyethylene oxide or polypropylene oxide with an amino group as an end group, and the number average molecular weight is 200-4000;
step 2, naturally cooling the polyol and the ether-based macromolecular diamine subjected to the vacuum-pumping treatment in the step 1 to 50-55 ℃, adding a solvent, diisocyanate, a first cross-linking agent, a hydrophilic chain extender and a catalyst into a reaction kettle by adopting a one-step feeding method, uniformly mixing, and then heating to 60-90 ℃ for reaction, wherein the reaction time is 2-10 hours; the solvent is acetone, dioxane or N, N-dimethylacetamide; the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate; the first cross-linking agent is N- [ (1, 1-dimethyl-2-acetyl) ethyl ] -beta-dihydroxyethylamino propionamide, N' -diacetone propionamido ethylenediamine or 5- [ bis (2-hydroxyethyl) amino ] -2-pentanone; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the catalyst is dibutyl tin dilaurate or stannous octoate;
step 3, naturally cooling to 50-55 ℃ after the reaction in the step 2, adding a solvent to reduce the viscosity of the system to be less than 10000mP.s, naturally cooling to 20-30 ℃, adding a neutralizer to react for 10-30 min, naturally cooling to 5-10 ℃, adding water to carry out high-speed stirring and emulsification to form polyurethane urea emulsion; the high-speed stirring speed is 1000-2000 revolutions per minute, and the emulsifying time is 10-30 min; the neutralizer is selected from triethylamine, sodium hydroxide or potassium hydroxide;
step 4, adding a second cross-linking agent into the polyurethane urea emulsion prepared in the step 3 for reaction, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed, wherein: the weight parts of the raw material components are as follows: 15-30 parts of polyol, 1-10 parts of ether-based macromolecular diamine, 10-30 parts of solvent, 10-30 parts of diisocyanate, 1-10 parts of first cross-linking agent, 3-8 parts of hydrophilic chain extender, 0.1-0.3 part of catalyst, 1-6 parts of neutralizer, 30-50 parts of water and 1-5 parts of second cross-linking agent; the second crosslinking agent is carbonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, succinic acid dihydrazide or isophthalic acid dihydrazide.
2. The waterborne polyurethane urea elastomer as claimed in claim 1, wherein the weight parts of the raw material components are as follows: 20-30 parts of polyol, 5-10 parts of ether-based macromolecular diamine, 20-30 parts of a solvent used in the step 2, 15-25 parts of diisocyanate, 3-8 parts of a first cross-linking agent, 5-8 parts of a hydrophilic chain extender, 0.1-0.3 part of a catalyst, 1-5 parts of a neutralizing agent, 40-50 parts of water and 2-5 parts of a second cross-linking agent.
3. The waterborne polyurethane urea elastomer of claim 1, wherein in step 1, the polyol and the ether-based macrodiamine are vacuumized at 90-120 ℃ for 1-2 h.
4. The aqueous polyurethane urea elastomer according to claim 1, wherein the reaction temperature in step 2 is 70 to 80 ℃ and the reaction time is 5 to 8 hours.
5. The aqueous polyurethane urea elastomer according to claim 1, wherein the solvent is added in step 3 to reduce the viscosity of the reaction system, the amount of the solvent is determined according to the viscosity test result of the reaction system, and the kind of the solvent added in step 3 is the same as that of the solvent added in step 2.
6. The aqueous polyurethane urea elastomer as claimed in claim 1, wherein the second crosslinking agent is added in step 4 to react while maintaining a high-speed stirring speed of 1000 to 2000 rpm for 10 to 30 min.
7. The preparation method of the waterborne polyurethane-urea elastomer is characterized by comprising the following steps: step 1, carrying out vacuum pumping treatment on polyhydric alcohol and ether-based macromolecular diamine at 90-120 ℃ to completely dehydrate and avoid the influence of water on the reaction; the polyalcohol is selected from poly adipic acid-1, 4-butanediol diol ester diol, polytetrahydrofuran ether diol or polypropylene oxide diol; the ether-based macromolecular diamine is polyethylene oxide or polypropylene oxide with an amino group as an end group, and the number average molecular weight is 200-4000;
step 2, naturally cooling the polyol and the ether-based macromolecular diamine subjected to the vacuum-pumping treatment in the step 1 to 50-55 ℃, adding a solvent, diisocyanate, a first cross-linking agent, a hydrophilic chain extender and a catalyst into a reaction kettle by adopting a one-step feeding method, uniformly mixing, and then heating to 60-90 ℃ for reaction, wherein the reaction time is 2-10 hours; the solvent is acetone, dioxane or N, N-dimethylacetamide; the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate; the first cross-linking agent is N- [ (1, 1-dimethyl-2-acetyl) ethyl ] -beta-dihydroxyethylamino propionamide, N' -diacetone propionamido ethylenediamine or 5- [ bis (2-hydroxyethyl) amino ] -2-pentanone; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the catalyst is dibutyl tin dilaurate or stannous octoate;
step 3, naturally cooling to 50-55 ℃ after the reaction in the step 2, adding a solvent to reduce the viscosity of the system to be less than 10000mP.s, naturally cooling to 20-30 ℃, adding a neutralizer to react for 10-30 min, naturally cooling to 5-10 ℃, adding water to carry out high-speed stirring and emulsification to form polyurethane urea emulsion; the high-speed stirring speed is 1000-2000 revolutions per minute, and the emulsifying time is 10-30 min; the neutralizer is selected from triethylamine, sodium hydroxide or potassium hydroxide;
step 4, adding a second cross-linking agent into the polyurethane urea emulsion prepared in the step 3 for reaction, and then pumping away the solvent in a vacuum state to obtain the polyurethane urea emulsion, namely the water phase emulsion in which the polyurethane urea elastomer is uniformly dispersed, wherein: the weight parts of the raw material components are as follows: 15-30 parts of polyol, 1-10 parts of ether-based macromolecular diamine, 10-30 parts of solvent, 10-30 parts of diisocyanate, 1-10 parts of first cross-linking agent, 3-8 parts of hydrophilic chain extender, 0.1-0.3 part of catalyst, 1-6 parts of neutralizer, 30-50 parts of water and 1-5 parts of second cross-linking agent; the second crosslinking agent is carbonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, succinic acid dihydrazide or isophthalic acid dihydrazide.
8. The preparation method of the waterborne polyurethane urea elastomer as claimed in claim 7, wherein the raw material components are as follows in parts by weight: 20-30 parts of polyol, 5-10 parts of ether-based macromolecular diamine, 20-30 parts of a solvent used in the step 2, 15-25 parts of diisocyanate, 3-8 parts of a first cross-linking agent, 5-8 parts of a hydrophilic chain extender, 0.1-0.3 part of a catalyst, 1-5 parts of a neutralizing agent, 40-50 parts of water and 2-5 parts of a second cross-linking agent.
9. The method of claim 7, wherein in step 1, the polyol and the ether-based macrodiamine are vacuumized at 90-120 ℃ for 1-2 hours.
10. The method of claim 7, wherein the reaction temperature is 70-80 ℃ and the reaction time is 5-8 hours in step 2.
11. The method of claim 7, wherein the solvent is added to reduce the viscosity of the reaction system in step 3, the amount of the solvent is determined according to the viscosity test result of the reaction system, and the solvent added in step 3 is the same as the solvent added in step 2.
12. The method of claim 7, wherein the second crosslinking agent is added to react in step 4, the stirring speed is kept at 1000-2000 rpm, and the reaction time is kept at 10-30 min.
13. Use of an aqueous polyurethaneurea elastomer according to any of claims 1 to 6 for the preparation of a track material.
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| CN101802040A (en) * | 2007-07-20 | 2010-08-11 | 因维斯塔技术有限公司 | Aqueous polyurethaneurea compositions including dispersions and film |
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| CN101802040A (en) * | 2007-07-20 | 2010-08-11 | 因维斯塔技术有限公司 | Aqueous polyurethaneurea compositions including dispersions and film |
| CN101580577A (en) * | 2009-06-18 | 2009-11-18 | 建德市顺发化工助剂有限公司 | Modified waterborne polyurethane resin for artificial leather and preparation method thereof |
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