Polyurethane material with high wear resistance and impact resistance and preparation method thereof

Abstract

The invention relates to the technical field of polyurethane materials, and discloses a high-wear-resistant impact-resistant polyurethane material and a preparation method thereof, and the high-wear-resistant impact-resistant polyurethane material is prepared from the following components: an oligomer nanocomposite, polyester polyol, isocyanate, a catalyst, a chain extender and dioctyl phthalate; the performance of the prepared polyurethane material is greatly improved, and particularly, the wear resistance and the impact resistance of the prepared polyurethane material are greatly improved, so that the requirements on the wear resistance and the impact resistance in the application field can be met. According to the invention, the prepared oligomer nano-composite is adopted to replace the conventional nano-filler, so that the wear resistance and impact resistance of the polyurethane material can be greatly improved. According to the invention, the introduced oligomer nano-composite can effectively enhance the interface bonding performance of the nano-auxiliary agent and a polyurethane matrix, so that the problem that the conventional nano-filler is not easy to disperse in the polyurethane material is effectively avoided, and the enhancement effect of the nano-filler is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane materials, and specifically to a highly wear-resistant and impact-resistant polyurethane material and a preparation method thereof. Background Art

[0002] Polyurethane (abbreviated as PU) is a polymer material formed by the polymerization reaction of isocyanate and polyol. Its molecular structure contains urethane groups (-NHCOO-), and it has various forms, including foams, elastomers, coatings, adhesives, and fibers, etc.

[0003] Polyurethane materials are applied in multiple industrial fields, including: 1. Construction industry: thermal insulation materials, sealants; 2. Automotive industry: seats and interiors, shock-absorbing components; 3. Furniture industry: soft foams, coatings and adhesives; 4. Electronics and electrical appliances: insulating materials, encapsulation materials; 5. Textile industry: synthetic leather, elastic fibers; 6. Medical field: medical catheters, artificial organs; 7. Sporting goods: sports shoes, protective equipment; 8. Other applications: coatings and adhesives, packaging materials: used for manufacturing cushioning packaging materials.

[0004] When applied in some fields, polyurethane materials are required to have higher wear resistance, while the wear resistance of polyurethane materials prepared by existing technologies is relatively general and cannot meet the requirements.

[0005] Based on this, we have proposed a highly wear-resistant and impact-resistant polyurethane material. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the present invention provides a highly wear-resistant and impact-resistant polyurethane material and a preparation method thereof.

[0007] To achieve the above object, the present invention provides the following technical solutions: A highly wear-resistant and impact-resistant polyurethane material is made from the following components by weight: 15-18 parts of oligomer nanocomposite, 30-35 parts of polyester polyol, 90-98 parts of isocyanate, 1-1.5 parts of catalyst, 5-8 parts of chain extender, and 3.2-3.5 parts of dioctyl phthalate.

[0008] As a further technical solution, the preparation method of the oligomer nanocomposite is as follows: First, add thiourea and ammonium molybdate hydrate to the reaction kettle, then add distilled water, stir at a speed of 500 r / min for 20 min, then heat to a temperature of 180 °C, keep stirring and reacting for 12 hours, cool to room temperature, then carry out suction filtration, wash with water, and then place it at 60 °C for drying for 2 hours to obtain a nano additive; Add hexamethyldisiloxane, phenyltrimethoxysilane, nano additive and concentrated sulfuric acid into the reaction kettle in sequence, then heat to 75 °C, stir and react for 30 min, then dropwise add distilled water while stirring, and finish dropping in 2 h; After refluxing and reacting for 2 h, obtain through drying.

[0009] As a further technical solution, the molar ratio of ammonium molybdate to thiourea is 1:3, and the mixing ratio of ammonium molybdate to distilled water is 15 g: 300 mL.

[0010] As a further technical solution, the mixing ratio of hexamethyldisiloxane, phenyltrimethoxysilane, nano additive, concentrated sulfuric acid and distilled water is 12 g: 5 g: 3 g: 30 mL: 100 mL; The mass fraction of the concentrated sulfuric acid is 90%.

[0011] As a further technical solution: The polyester polyol used is: polyethylene adipate; The number average molecular weight is 5000, and the hydroxyl value is 350 mg KOH / g.

[0012] As a further technical solution: The isocyanate is 4,4'-diphenylmethane diisocyanate.

[0013] As a further technical solution: The catalyst is dibutyltin dilaurate; The chain extender is ethylenediamine.

[0014] A preparation method of a high wear-resistant and impact-resistant polyurethane material, comprising the following steps: Prepare materials: Weigh respectively according to the components of each weight part: oligomer nano complex, polyester polyol, isocyanate, catalyst dibutyltin dilaurate, chain extender, dioctyl phthalate; Prepolymerization reaction: Mix the polyester polyol and the isocyanate under nitrogen protection, control the reaction temperature at 75 °C, stir and react for 4 hours to obtain a prepolymer; Dispersion: After the above prepolymer is formed, slowly add the oligomer nano complex to the prepolymer, and then carry out high-speed stirring for 20 min to obtain a mixed material; Among them, the stirring speed is 5500 r / min; Addition of catalyst: Add the catalyst, chain extender, dioctyl phthalate to the mixed material, and then continue to stir for 30 min to obtain a uniformly dispersed material; Pouring and molding: Pour the above obtained uniformly dispersed material into a mold, and cure at a temperature of 30 - 35 °C for 24 hours to obtain a preliminarily cured part; Post-curing treatment: Carry out strengthening curing treatment on the preliminarily cured part at a temperature of 122 - 125 °C for 4 - 5 hours to obtain a secondarily cured part; Vacuum curing: Place the obtained secondary cured part in a vacuum environment for further curing treatment, and then discharge the material to obtain...

[0015] As a further technical solution: The vacuum degree of the vacuum environment is 0.1 Pa.

[0016] Compared with the prior art, the present invention provides a highly wear-resistant and impact-resistant polyurethane material, having the following beneficial effects: The performance of the polyurethane material prepared by the present invention is greatly improved. In particular, the wear resistance and impact resistance of the prepared polyurethane material are significantly improved, so as to meet the requirements for wear resistance and impact resistance in the application field.

[0017] By using the prepared oligomer nanocomposite to replace the conventional nano-fillers, the present invention can greatly improve the wear resistance and impact resistance of the polyurethane material. By introducing the oligomer nanocomposite, the present invention can effectively enhance the interfacial bonding performance between the nano-additives and the polyurethane matrix. Thus, the problem that the conventional nano-fillers are not easily dispersed in the polyurethane material is effectively avoided, and the enhancement effect is improved. It is more uniformly distributed in the polyurethane matrix, and because a more stable microstructure can be formed, the prepared polyurethane material can be more impact-resistant.

[0018] Moreover, through the combined action of the oligomer nanocomposite and other components, the toughness of the polyurethane material can be optimized, so that the prepared polyurethane material can exhibit better anti-fracture performance when being impacted.

[0019] Through the synergistic effect among the components in the oligomer nanocomposite, the damping performance of the polyurethane material can be greatly improved, so that it exhibits better wear resistance and impact resistance under dynamic loads.

[0020] The polyurethane material prepared by the present invention can have a longer service life under cyclic loads, further broadening its application field. Specific embodiments

[0021] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0022] Example 1

[0023] A preparation method of a highly wear-resistant and impact-resistant polyurethane material, comprising the following steps: Preparation of materials: Weigh the components according to the respective weight parts: 15 parts of oligomer nanocomposite, 30 parts of polyester polyol, 90 parts of isocyanate, 1 part of catalyst, 5 parts of chain extender, and 3.2 parts of dioctyl phthalate; the preparation method of the oligomer nanocomposite is as follows: First, add thiourea and ammonium molybdate hydrate to the reaction kettle, then add distilled water, stir at a speed of 500 r / min for 20 min, then heat to a temperature of 180 °C, keep stirring and reacting for 12 hours, cool to room temperature, filter by suction, wash with water, and then dry at 60 °C for 2 hours to obtain a nano - additive; Add hexamethyldisiloxane, phenyltrimethoxysilane, nano - additive, and concentrated sulfuric acid to the reaction kettle in sequence, then heat to 75 °C, stir and react for 30 min, then dropwise add distilled water while stirring, and finish dropping in 2 h; After refluxing and reacting for 2 h, through drying, we get; the molar ratio of ammonium molybdate to thiourea is 1:3, and the mixing ratio of ammonium molybdate and distilled water is 15 g:300 mL; the mixing ratio of hexamethyldisiloxane, phenyltrimethoxysilane, nano - additive, concentrated sulfuric acid, and distilled water is 12 g:5 g:3 g:30 mL:100 mL; The mass fraction of the concentrated sulfuric acid is 90%; the polyester polyol used is: polyethylene adipate; The number - average molecular weight is 5000, and the hydroxyl value is 350 mg KOH / g; the isocyanate is 4,4'-diphenylmethane diisocyanate; the catalyst is dibutyltin dilaurate; The chain extender is ethylenediamine; Pre - polymerization reaction: Under nitrogen protection, mix the polyester polyol and isocyanate, control the reaction temperature at 75 °C, stir and react for 4 hours to obtain a prepolymer; Dispersion: After the above prepolymer is formed, slowly add the oligomer nanocomposite to the prepolymer, and then carry out high - speed stirring for 20 min to obtain a mixed material; Among them, the stirring speed is 5500 r / min; Addition of catalyst: Add the catalyst, chain extender, and dioctyl phthalate to the mixed material, and then continue to stir for 30 min to obtain a uniformly dispersed material; Casting and molding: Pour the uniformly dispersed material obtained above into a mold, cure at a temperature of 30 °C for 24 hours to obtain a preliminarily cured part; Post - curing treatment: Carry out strengthening curing treatment on the preliminarily cured part at a temperature of 122 °C for 4 hours to obtain a secondarily cured part; Vacuum curing: Place the obtained secondarily cured part in a vacuum environment for re - curing treatment, and then discharge to obtain; the vacuum degree of the vacuum environment is 0.1 Pa.

[0024] Example 2

[0025] A preparation method of a highly wear-resistant and impact-resistant polyurethane material, comprising the following steps: Material preparation: Weigh according to the components of each weight part: 16 parts of oligomer nanocomposite, 32 parts of polyester polyol, 93 parts of isocyanate, 1.2 parts of catalyst, 6 parts of chain extender, 3.3 parts of dioctyl phthalate; The preparation method of the oligomer nanocomposite is: First, add thiourea and ammonium molybdate hydrate to the reaction kettle, then add distilled water, stir at a speed of 500 r / min for 20 min, then heat to a temperature of 180 °C, keep stirring and reacting for 12 hours, cool to room temperature, filter by suction, wash with water, and then dry at 60 °C for 2 hours to obtain a nano additive; Add hexamethyldisiloxane, phenyltrimethoxysilane, nano additive and concentrated sulfuric acid to the reaction kettle in sequence, then heat to 75 °C, stir and react for 30 min, then dropwise add distilled water while stirring, and finish dropping in 2 h; After refluxing and reacting for 2 h, through drying, obtain; The molar ratio of ammonium molybdate to thiourea is 1:3, and the mixing ratio of ammonium molybdate and distilled water is 15 g: 300 mL; The mixing ratio of hexamethyldisiloxane, phenyltrimethoxysilane, nano additive, concentrated sulfuric acid and distilled water is 12 g: 5 g: 3 g: 30 mL: 100 mL; The mass fraction of the concentrated sulfuric acid is 90%; The polyester polyol used is: polyethylene adipate; The number average molecular weight is 5000, and the hydroxyl value is 350 mg KOH / g; The isocyanate is 4,4'-diphenylmethane diisocyanate; The catalyst is dibutyltin dilaurate; The chain extender is ethylenediamine; Prepolymerization reaction: Mix polyester polyol and isocyanate under nitrogen protection, control the reaction temperature at 75 °C, stir and react for 4 hours to obtain a prepolymer; Dispersion: After the above prepolymer is formed, slowly add the oligomer nanocomposite to the prepolymer, and then carry out high-speed stirring for 20 min to obtain a mixture; Among them, the stirring speed is 5500 r / min; Addition of catalyst: Add catalyst, chain extender and dioctyl phthalate to the mixture, and then continue to stir for 30 min to obtain a uniformly dispersed material; Casting and molding: Pour the uniformly dispersed material obtained above into a mold, cure at a temperature of 32 °C for 24 hours to obtain a preliminarily cured part; Post-curing treatment: Carry out enhanced curing treatment on the preliminarily cured part at a temperature of 123 °C for 4.5 hours to obtain a secondary cured part; Vacuum curing: Place the obtained secondary cured part in a vacuum environment for further curing treatment, and then discharge the material to obtain; the vacuum degree of the vacuum environment is 0.1 Pa.

[0026] Example 3

[0027] A preparation method of a highly wear-resistant and impact-resistant polyurethane material, comprising the following steps: Material preparation: Weigh according to each component by weight: 18 parts of oligomer nanocomposite, 35 parts of polyester polyol, 98 parts of isocyanate, 1.5 parts of catalyst, 8 parts of chain extender, 3.5 parts of dioctyl phthalate; the preparation method of the oligomer nanocomposite is: First, add thiourea and ammonium molybdate hydrate to the reaction kettle, then add distilled water, stir at a speed of 500 r / min for 20 min, then heat to a temperature of 180 °C, keep stirring and reacting for 12 hours, cool to room temperature, filter by suction, wash with water, and then place at 60 °C for drying for 2 hours to obtain a nano additive; Add hexamethyldisiloxane, phenyltrimethoxysilane, nano additive and concentrated sulfuric acid to the reaction kettle in sequence, then heat to 75 °C, stir and react for 30 min, then dropwise add distilled water, stir while dropping, and finish dropping in 2 h; After refluxing and reacting for 2 h, through drying, obtain; the molar ratio of ammonium molybdate to thiourea is 1:3, and the mixing ratio of ammonium molybdate and distilled water is 15 g: 300 mL; the mixing ratio of hexamethyldisiloxane, phenyltrimethoxysilane, nano additive, concentrated sulfuric acid and distilled water is 12 g: 5 g: 3 g: 30 mL: 100 mL; The mass fraction of the concentrated sulfuric acid is 90%; the polyester polyol used is: polyethylene adipate; The number average molecular weight is 5000, and the hydroxyl value is 350 mg KOH / g; the isocyanate is 4,4'-diphenylmethane diisocyanate; the catalyst is dibutyltin dilaurate; The chain extender is ethylenediamine; Prepolymerization reaction: Mix the polyester polyol and the isocyanate under nitrogen protection, control the reaction temperature at 75 °C, and stir and react for 4 hours to obtain a prepolymer; Dispersion: After the above prepolymer is formed, slowly add the oligomer nanocomposite to the prepolymer, and then carry out high-speed stirring for 20 min to obtain a mixed material; Among them, the stirring speed is 5500 r / min; Addition of catalyst: Add the catalyst, chain extender, and dioctyl phthalate to the mixed material, and then continue to stir for 30 min to obtain a uniformly dispersed material; Casting and molding: Pour the uniformly dispersed material obtained above into a mold, cure at a temperature of 35 °C for 24 hours to obtain a preliminarily cured part; Post-curing treatment: The preliminarily cured parts are subjected to enhanced curing treatment at a temperature of 125 °C for 5 hours to obtain secondarily cured parts; Vacuum curing: The obtained secondarily cured parts are placed in a vacuum environment for re-curing treatment, and then discharged to obtain; the vacuum degree of the vacuum environment is 0.1 Pa.

[0028] The following are comparative examples: Comparative Example 1: On the basis of Example 1, the oligomer nanocomposite is replaced with an equal amount of nano-silica, and the rest of the technical solutions are the same as those of Example 1.

[0029] Comparative Example 2: On the basis of Example 1, the oligomer nanocomposite is not added, and the rest of the technical solutions are the same as those of Example 1.

[0030] Test: Perform performance detection on the specimens of the examples and comparative examples: Shore hardness: Refer to ASTM D624; Table 1 Shore A hardness Example 1 76 Example 2 74 Example 3 76 Comparative Example 1 71 Comparative Example 2 68 As can be seen from Table 1, the polyurethane material prepared by the present invention has a relatively high surface hardness.

[0031] Wear resistance test, refer to ISO4649; Table 2 Wear mm³ Example 1 45 Example 2 47 Example 3 44 Comparative Example 1 52 Comparative Example 2 63 As can be seen from Table 2, the polyurethane material prepared by the present invention has good wear resistance.

[0032] Perform impact resistance test on the polyurethane materials of the examples and comparative examples, refer to GB / T 1843: Table 3 Impact strength kJ / m² Example 1 185.3 Example 2 186.0 Example 3 184.9 Comparative Example 1 156.3 Comparative Example 2 127.1 As can be seen from Table 3, the polyurethane material of the present invention has excellent impact resistance.

[0033] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A highly wear-resistant and impact-resistant polyurethane material, characterized in that: The invention comprises the following ingredients by weight: 15-18 parts of oligomer nanocomposite, 30-35 parts of polyester polyol, 90-98 parts of isocyanate, 1-1.5 parts of catalyst, 5-8 parts of chain extender and 3.2-3.5 parts of dioctyl phthalate.

2. A highly wear-resistant and impact-resistant polyurethane material according to claim 1, characterized in that: The preparation method of the oligomer nanocomposite is as follows: First, thiourea and hydrated ammonium molybdate were added to a reaction kettle, and then distilled water was added, stirred at a speed of 500 r / min for 20 minutes, heated to 180°C, stirred and reacted for 12 hours, cooled to room temperature, filtered, washed with water, and then dried at 60°C for 2 hours to obtain a nano-additive; Hexamethyldisiloxane, phenyltrimethoxysilane, nano-additive and concentrated sulfuric acid were added to the reaction kettle in sequence, and then heated to 75°C, stirred for reaction for 30 minutes, and then distilled water was added dropwise, stirring while adding, and the addition was completed within 2 hours; After reflux reaction for 2 h, the product was obtained after drying.

3. A highly wear-resistant and impact-resistant polyurethane material according to claim 2, characterized in that: The molar ratio of ammonium molybdate to thiourea is 1:3, and the mixing ratio of ammonium molybdate to distilled water is 15g:300mL.

4. A highly wear-resistant and impact-resistant polyurethane material according to claim 2, characterized in that: The mixing ratio of hexamethyldisiloxane, phenyltrimethoxysilane, nano additive, concentrated sulfuric acid and distilled water is 12g:5g:3g:30mL:100mL; The mass fraction of the concentrated sulfuric acid is 90%.

5. The highly wear-resistant and impact-resistant polyurethane material according to claim 1, characterized in that: The polyester polyol adopts: polyethylene adipate; The number average molecular weight is 5000 and the hydroxyl value is 350 mgKOH / g.

6. The highly wear-resistant and impact-resistant polyurethane material according to claim 5, characterized in that: The isocyanate is 4,4'-diphenylmethane diisocyanate.

7. The highly wear-resistant and impact-resistant polyurethane material according to claim 5, characterized in that: The catalyst is dibutyltin dilaurate; The chain extender is ethylenediamine.

8. The method for preparing a highly wear-resistant and impact-resistant polyurethane material according to claim 1, characterized in that: The following steps are involved: Preparation: Weigh the following components by weight: oligomer nanocomposite, polyester polyol, isocyanate, catalyst dibutyltin dilaurate, chain extender, dioctyl phthalate; Prepolymerization: Mix polyester polyol and isocyanate under nitrogen protection, control the reaction temperature at 75°C, stir and react for 4 hours to obtain a prepolymer; Dispersion: After the above prepolymer is formed, slowly add the oligomer nanocomposite to the prepolymer, and then stir at high speed for 20 minutes to obtain a mixture; Among them, the stirring speed is 5500r / min; Addition of catalyst: Add catalyst, chain extender and dioctyl phthalate to the mixture, and then continue stirring for 30 minutes to obtain a uniformly dispersed material; Casting: pour the uniformly dispersed material obtained above into a mold and cure it at 30-35°C for 24 hours to obtain a preliminary cured part; Post-curing treatment: The primary cured part is subjected to an intensive curing treatment at a temperature of 122-125°C for 4-5 hours to obtain a secondary cured part; Vacuum curing: The obtained secondary cured part is placed in a vacuum environment for re-curing treatment, and then discharged to obtain.

9. The method for preparing a highly wear-resistant and impact-resistant polyurethane material according to claim 8, characterized in that: The vacuum degree of the vacuum environment is 0.1Pa.