Impact-resistant elastic silicon PU material for plastic track and preparation method of impact-resistant elastic silicon PU material

Abstract

The invention relates to the technical field of polyurethane plastics, and discloses an impact-resistant elastic silicon PU (polyurethane) material for a plastic runway and a preparation method of the impact-resistant elastic silicon PU material. The PU material comprises the following raw materials: a component A, 100 parts of polyether polyol, 25-40 parts of filler and 10-30 parts of an organic silicon toughening agent, and the component B comprises the following components in parts by weight: 100 parts of polyether polyol and 68-75 parts of diphenylmethane-4, 4 '-diisocyanate. The organic silicon toughening agent disclosed by the invention has good compatibility with polyurethane, can be uniformly dispersed in a polyurethane matrix, contains a flexible siloxane structure, has a good toughening effect on polyurethane, and remarkably improves the impact strength, bending strength and wear resistance of the PU material. And the organic silicon toughening agent contains a high-temperature-resistant phthalazinone structure, so that the thermal decomposition temperature and the heat resistance of the material can be improved when the organic silicon toughening agent is added into polyurethane.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane plastics, and specifically relates to a silicone PU material for a plastic runway with impact resistance and elasticity and a preparation method thereof. Background Art

[0002] Plastic runways are common sports facilities, and their main materials include polyvinyl chloride, polyurethane, rubber, etc. Among them, polyurethane is non-toxic, odorless, has high elasticity, good low-temperature resistance, and excellent aging resistance, and can be made into elastomers, foams, plastics and other products, which are widely used in industries such as plastic runways, sports goods, electronic appliances, and the automotive industry. Improving the impact resistance, heat resistance, wear resistance and other properties of polyurethane and its elastomer materials can make them have better practical applications in materials such as plastic runways.

[0003] Siloxane substances have excellent toughness, wear resistance, chemical resistance and anti-corrosion properties, and have important applications in polymer materials such as polyurethane, polyethylene, and rubber. Chinese Patent CN119039766B discloses an environmentally friendly high-elastic polyurethane-modified acrylic runway surface glue and a preparation method thereof. Using acrylate compounds, methyltrimethoxysilane, octamethylcyclotetrasiloxane, waterborne polyurethane emulsion and other raw materials, the prepared polyurethane-modified acrylic runway surface glue has advantages such as high elasticity and good tensile properties. However, the thermal decomposition weight loss temperature of the polyurethane runway surface glue of this patent is relatively low, and the impact strength and bending strength of polyurethane are not improved. Summary of the Invention

[0004] The present invention solves the problems of poor elasticity, impact resistance and wear resistance of polyurethane materials used for plastic runways.

[0005] The technical solution of the present invention: A silicone PU material for a plastic runway with impact resistance and elasticity, by weight fraction, the raw materials of the silicone PU material include component A and component B.

[0006] Component A is made from the following raw materials: 100 parts of polyether polyol, 25-40 parts of filler, 1.2-2 parts of dibutyltin dilaurate, 1-1.8 parts of antioxidant, 10-30 parts of organosilicon toughening agent.

[0007] Component B is made from the following raw materials: 100 parts of polyether polyol, 68-75 parts of diphenylmethane-4,4'-diisocyanate.

[0008] Furthermore, a preparation method of the silicone PU material is characterized in that the preparation method is:

[0009] (1) Introduce nitrogen into the reaction kettle, add the raw materials of component B, polyether polyol and diphenylmethane-4,4'-diisocyanate, heat to 70-75 °C, and react for 2-3 h to obtain a polyurethane prepolymer.

[0010] (2) Add polyether polyol, filler, dibutyltin dilaurate, antioxidant, and silicone toughening agent into a container, stir and mix evenly to obtain Component A; then add Component A and polyurethane prepolymer into a mold, first cure thermally at 100 - 110 °C for 1 - 2 h, then perform heat treatment at 110 - 120 °C for 12 - 18 h, and cool to obtain the silicone PU material for a shock-resistant elastic plastic runway.

[0011] Further, the polyether polyol is polyethylene glycol, polypropylene glycol, or polytetrahydrofuran ether diol.

[0012] Further, the filler is montmorillonite, talcum powder, or calcium carbonate fine powder.

[0013] Further, the preparation method of acrylate-based phthalazinone is as follows: Add a solvent, 100 parts (by weight) of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 130 - 144 parts of isocyanatoethyl methacrylate, and 0.24 - 0.36 parts of dibutyltin dilaurate into a reaction vessel, introduce nitrogen, react at 60 - 70 °C for 1 - 1.5 h, perform vacuum distillation, wash the product with n-hexane, and then recrystallize with ethanol to obtain acrylate-based phthalazinone. The reaction formula is:

[0014]

[0015] Further, the solvent is tetrahydrofuran or toluene.

[0016] Further, the preparation method of the silicone toughening agent is as follows: Add tetrahydrofuran, 100 parts (by weight) of acrylate-based phthalazinone, 24 - 28 parts of 1,1,3,3-tetramethyldisiloxane, and an isopropanol solution containing 0.9 - 1.3 parts of chloroplatinic acid into a reaction vessel, introduce nitrogen, heat to 60 - 70 °C, and perform condensation reflux reaction for 6 - 10 h, perform vacuum distillation, wash the product with ethanol, and dry to obtain the silicone toughening agent. The reaction formula is:

[0017]

[0018] The technical effects of the present invention: The present invention utilizes the hydrosilylation polymerization reaction of acrylate-based phthalazinone and 1,1,3,3-tetramethyldisiloxane to obtain a silicone toughening agent containing a phthalazinone structure, and then uses it together with polyether polyol, montmorillonite and other fillers as Component A of polyurethane. Component B is a terminal isocyanate prepolymer prepared by reacting polyether polyol and diphenylmethane - 4,4'-diisocyanate, and is formed by thermal curing to obtain the silicone PU material for a plastic runway.

[0019] The silicone toughening agent of the present invention contains the same urethane groups as polyurethane, has a similar polarity to PU polyurethane, and contains urea groups at the same time, which can form stable hydrogen bond interactions with polyurethane, resulting in good compatibility between the silicone toughening agent and polyurethane and enabling it to be evenly dispersed in the polyurethane matrix. The silicone toughening agent contains a flexible siloxane structure, which plays a good toughening role on polyurethane, significantly improving the impact strength and flexural strength of the PU material, reducing the wear volume of the PU material, and enhancing the wear resistance. In addition, the silicone toughening agent contains a phthalazinone structure with high temperature resistance, and when added to polyurethane, it can increase the thermal decomposition temperature and heat resistance of the material. Specific embodiments

[0020] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0021] Example 1:

[0022] (1) Add 80 mL of toluene, 5 g (21 mmol) of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 7.2 g of isocyanatoethyl methacrylate, and 0.012 g of dibutyltin dilaurate to a reaction vessel, introduce nitrogen, react at 65 °C for 1.5 h, carry out vacuum distillation, wash the product with n-hexane, and then recrystallize with ethanol to obtain acrylate-based phthalazinone.

[0023] (2) Add 250 mL of tetrahydrofuran, 10 g of acrylate-based phthalazinone, 2.4 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.13 g of chloroplatinic acid to a reaction vessel, introduce nitrogen, heat to 60 °C, carry out condensation reflux reaction for 10 h, carry out vacuum distillation, wash the product with ethanol, and dry to obtain a silicone toughening agent.

[0024] (3) Introduce nitrogen into a reaction kettle, add 100 g of polytetrahydrofuran ether glycol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in component B, heat to 75 °C, and react for 2 h to obtain a polyurethane prepolymer.

[0025] (4) Add 100 g of polytetrahydrofuran ether glycol 1000, 40 g of filler calcium carbonate fine powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 10 g of silicone toughening agent to a container, stir and mix evenly to obtain component A; then add component A and the polyurethane prepolymer to a mold, first cure thermally at 110 °C for 1 h, then heat-treat at 120 °C for 12 h, and cool to obtain a silicone PU material for a shock-resistant elastic plastic runway.

[0026] Example 2:

[0027] (1) Add 100 mL of tetrahydrofuran, 5 g of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 6.5 g of isocyanatoethyl methacrylate, and 0.018 g of dibutyltin dilaurate to the reaction vessel. Introduce nitrogen gas, and carry out a reflux reaction at 60 °C for 1.5 h. Then perform vacuum distillation, wash the product with n-hexane, and recrystallize it with ethanol to obtain acrylate-based phthalazinone.

[0028] (2) Add 300 mL of tetrahydrofuran, 10 g (18.25 mmol) of acrylate-based phthalazinone, 2.8 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.13 g of chloroplatinic acid to the reaction vessel. Introduce nitrogen gas, heat to 60 °C, and carry out a reflux reaction for 10 h. Then perform vacuum distillation, wash the product with ethanol, and dry it to obtain an organosilicon toughening agent.

[0029] (3) Introduce nitrogen gas into the reaction kettle, add 100 g of polyethylene glycol 1000 and 75 g of diphenylmethane-4,4'-diisocyanate as Component B, heat to 70 °C, and react for 3 h to obtain a polyurethane prepolymer.

[0030] (4) Add 100 g of polyethylene glycol 1000, 25 g of filler montmorillonite, 2 g of dibutyltin dilaurate, 1.3 g of antioxidant 1010, and 15 g of organosilicon toughening agent to the container, stir and mix evenly to obtain Component A; then add Component A and the polyurethane prepolymer to the mold, first cure thermally at 100 °C for 2 h, then perform heat treatment at 110 °C for 18 h, and cool to obtain a silicone-PU material for shock-resistant elastic plastic runway.

[0031] Example 3:

[0032] (1) Add 80 mL of toluene, 5 g of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 6.8 g of isocyanatoethyl methacrylate, and 0.012 g of dibutyltin dilaurate to the reaction vessel. Introduce nitrogen gas, and react at 70 °C for 1 h. Then perform vacuum distillation, wash the product with n-hexane, and recrystallize it with ethanol to obtain acrylate-based phthalazinone.

[0033] (2) Add 300 mL of tetrahydrofuran, 10 g of acrylate-based phthalazinone, 2.6 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.012 g of chloroplatinic acid to the reaction vessel. Introduce nitrogen gas, heat to 70 °C, and carry out a reflux reaction for 6 h. Then perform vacuum distillation, wash the product with ethanol, and dry it to obtain an organosilicon toughening agent.

[0034] (3) Nitrogen is introduced into the reaction kettle, and 100 g of polypropylene glycol 1000 and 68 g of diphenylmethane-4,4'-diisocyanate in Component B are added. It is heated to 75 °C and reacted for 2 h to obtain a polyurethane prepolymer.

[0035] (4) 100 g of polypropylene glycol 1000, 28 g of filler talc powder, 1.2 g of dibutyltin dilaurate, 1 g of antioxidant 1010, and 20 g of silicone toughening agent are added to a container and stirred evenly to obtain Component A; then Component A and the polyurethane prepolymer are added to a mold, first heat-cured at 100 °C for 2 h, then heat-treated at 120 °C for 12 h, and cooled to obtain a silicone PU material for a shock-resistant elastic plastic runway.

[0036] Example 4:

[0037] (1) 100 g of polytetrahydrofuran ether glycol 1000, 40 g of filler calcium carbonate fine powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 25 g of silicone toughening agent (prepared in the same way as in Example 1) are added to a container and stirred evenly to obtain Component A; then Component A and the polyurethane prepolymer (prepared in the same way as in Example 1) are added to a mold, first heat-cured at 110 °C for 1 h, then heat-treated at 120 °C for 12 h, and cooled to obtain a silicone PU material for a shock-resistant elastic plastic runway.

[0038] Example 5:

[0039] (1) 100 g of polytetrahydrofuran ether glycol 1000, 40 g of filler calcium carbonate fine powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 30 g of silicone toughening agent (prepared in the same way as in Example 1) are added to a container and stirred evenly to obtain Component A; then Component A and the polyurethane prepolymer (prepared in the same way as in Example 1) are added to a mold, first heat-cured at 110 °C for 1 h, then heat-treated at 120 °C for 12 h, and cooled to obtain a silicone PU material for a shock-resistant elastic plastic runway.

[0040] Comparative Example 1:

[0041] (1) Nitrogen is introduced into the reaction kettle, and 100 g of polytetrahydrofuran ether glycol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in the raw materials of Component B are added. It is heated to 75 °C and reacted for 2 h to obtain a polyurethane prepolymer.

[0042] (2) Add 100 g of polytetrahydrofuran ether diol 1000, 40 g of filler calcium carbonate fine powder, 1.5 g of dibutyltin dilaurate, and 1.8 g of antioxidant 1010 to the container, stir and mix evenly to obtain Component A; then add Component A and the polyurethane prepolymer to the mold, first cure thermally at 110 °C for 1 h, then heat-treat at 120 °C for 12 h, and cool to obtain the silicone PU material for plastic runway.

[0043] Comparative Example 2:

[0044] (1) Add 250 mL of tetrahydrofuran, 3.98 g (18.25 mmol) of butyl terephthalate (structural formula is CAS No. 6729-79-9), 2.4 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of isopropanol solution containing 0.13 g of chloroplatinic acid to the reaction vessel, introduce nitrogen, heat to 60 °C, carry out reflux reaction for 10 h, distill under reduced pressure, wash the product with ethanol, and dry to obtain the organosilicon toughening agent.

[0045] (2) Introduce nitrogen into the reaction kettle, add 100 g of polytetrahydrofuran ether diol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in the raw materials of Component B, heat to 75 °C, and react for 2 h to obtain the polyurethane prepolymer.

[0046] (3) Add 100 g of polytetrahydrofuran ether diol 1000, 40 g of filler calcium carbonate fine powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 10 g of organosilicon toughening agent to the container, stir and mix evenly to obtain Component A; then add Component A and the polyurethane prepolymer to the mold, first cure thermally at 110 °C for 1 h, then heat-treat at 120 °C for 12 h, and cool to obtain the silicone PU material for plastic runway.

[0047] Comparative Example 3:

[0048] (1) Add 80 mL of toluene, 2.29 g (21 mmol) of p-aminophenol (structural formula ), 7.2 g of isocyanatoethyl methacrylate, and 0.012 g of dibutyltin dilaurate to the reaction vessel, introduce nitrogen, react at 65 °C for 1.5 h, distill under reduced pressure, wash the product with n-hexane, and then recrystallize with ethanol to obtain the acrylate-based compound. The structural formula is:

[0049]

[0050] (2) Add 250 mL of tetrahydrofuran, 7.65 g (18.25 mmol) of acrylate-based compound, 2.4 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of isopropanol solution containing 0.13 g of chloroplatinic acid into the reaction vessel. Introduce nitrogen gas, heat to 60 °C, and carry out a condensation reflux reaction for 10 h. Then perform vacuum distillation, wash the product with ethanol, and dry it to obtain the silicone toughening agent.

[0051] (3) Introduce nitrogen gas into the reaction kettle, add 100 g of polytetrahydrofuran ether diol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in the B-component raw materials, heat to 75 °C, and react for 2 h to obtain the polyurethane prepolymer.

[0052] (4) Add 100 g of polytetrahydrofuran ether diol 1000, 40 g of filler calcium carbonate fine powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 10 g of silicone toughening agent into the container, stir and mix evenly to obtain the A-component; then add the A-component and the polyurethane prepolymer into the mold, first cure thermally at 110 °C for 1 h, then perform heat treatment at 120 °C for 12 h, and cool to obtain the silicone-PU material for plastic runway.

[0053] The impact performance and flexural strength of the PU material are tested according to the standard of GB / T 2567-2021. The wear resistance is tested according to the standard of GB / T1689-2014.

[0054] Thermogravimetric performance test: Weigh 8 mg of the PU material and place it in a thermogravimetric analyzer. Under a nitrogen atmosphere, heat it at a heating rate of 10 °C / min to 700 °C. T 5％ is the temperature at which 5% of the mass thermal decomposition occurs. T max is the temperature at which the mass thermal decomposition rate is the maximum.

[0055] Table 1 Performance test of PU material

[0056]

[0057]

[0058] As can be seen from the above table, a silicone toughening agent is added to the PU materials of Examples 1-5. It contains the same urethane group (-O-CO=NH) as polyurethane, which is similar in polarity to PU polyurethane. At the same time, it contains a urea group (N-CO-NH), which can form a stable hydrogen bond interaction with polyurethane, enabling good compatibility between the silicone toughening agent and polyurethane and allowing it to be evenly dispersed in the polyurethane matrix. The silicone toughening agent contains a flexible siloxane structure, which has a good toughening effect on polyurethane, significantly improving the impact strength and flexural strength of the PU material, reducing the wear volume of the PU material, and enhancing the wear resistance. At the same time, the silicone toughening agent contains a phthalazinone structure with high temperature resistance. When added to polyurethane, it can improve the heat resistance of the material and has a higher thermal decomposition temperature.

[0059] In Comparative Example 1, no silicone toughening agent was added, resulting in lower impact strength and flexural strength of the polyurethane PU material, a larger wear volume, and poor wear resistance. And T 5％ and T max are lower, and the heat resistance is poor.

[0060] In Comparative Example 2, using butyl terephthalate as the raw material, the prepared silicone toughening agent does not contain urethane groups and urea groups, has poor compatibility with polyurethane, and has poor toughening effect. Moreover, it does not contain a phthalazinone structure with high temperature resistance, and the thermal decomposition temperature of the PU material is low, resulting in poor heat resistance.

[0061] The acrylate-based compound and silicone toughening agent prepared in Comparative Example 3 do not contain a phthalazinone structure with high temperature resistance, resulting in a low thermal decomposition temperature of the PU material and poor heat resistance.

[0062] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A silicon PU material for an impact-resistant and elastic plastic runway, characterized in that: The raw materials of the silicon PU material include component A and component B by weight; Component A is made of the following raw materials: 100 parts of polyether polyol, 25-40 parts of filler, 1.2-2 parts of dibutyltin dilaurate, 1-1.8 parts of antioxidant, and 10-30 parts of silicone toughening agent; Component B is made from the following raw materials: 100 parts of polyether polyol, 68-75 parts of diphenylmethane-4,4'-diisocyanate; The preparation method of the organosilicon toughening agent is as follows: tetrahydrofuran and a structural formula of The isopropanol solution of acrylated phthalazinone, 1,1,3,3-tetramethyldisiloxane and chloroplatinic acid is introduced with nitrogen, and after the reaction, the product is distilled under reduced pressure, and the product is washed with ethanol and dried to obtain an organosilicon toughening agent.

2. According to the impact-resistant and elastic silicon PU material for plastic runway of claim 1, the polyether polyol is polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

3. The impact-resistant and elastic silicon PU material for plastic track according to claim 1, wherein the filler is montmorillonite, talcum powder or calcium carbonate powder.

4. The impact-resistant and elastic silicon PU material for plastic runway according to claim 1, characterized in that: In the preparation method of the organosilicon toughening agent, the reaction temperature is 60-70° C. and the reaction time is 6-10 hours.

5. The impact-resistant and elastic silicon PU material for plastic runway according to claim 1, characterized in that: By weight, the amount of the acrylate-based phthalazinone is 100 parts, the amount of 1,1,3,3-tetramethyldisiloxane is 24-28 parts, and the amount of chloroplatinic acid is 0.9-1.3 parts.

6. The impact-resistant and elastic silicon PU material for plastic runway according to claim 1, characterized in that: The preparation method of the acrylated phthalazinone comprises the following steps: adding a solvent, 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, isocyanoethyl methacrylate and dibutyltin dilaurate into a reaction container, introducing nitrogen, reacting at 60-70° C. for 1-1.5 hours, performing reduced pressure distillation, washing the product with n-hexane, and then recrystallizing with ethanol to obtain the acrylated phthalazinone.

7. The impact-resistant and elastic silicon PU material for plastic track according to claim 6, wherein the solvent is tetrahydrofuran or toluene.

8. The impact-resistant and elastic silicon PU material for plastic runway according to claim 6, characterized in that: By weight, the amount of 4-(4-hydroxyphenyl)-2,3-naphthyridin-1-one is 100 parts, the amount of isocyanatoethyl methacrylate is 130-144 parts, and the amount of dibutyltin dilaurate is 0.24-0.36 parts.

9. A method for preparing the impact-resistant elastic silicon PU material for plastic track according to any one of claims 1 to 8, characterized in that: The preparation method is: (1) introducing nitrogen into a reaction kettle, adding polyether polyol (component B) and diphenylmethane-4,4'-diisocyanate, heating to 70-75° C., reacting for 2-3 hours, and obtaining a polyurethane prepolymer; (2) Add polyether polyol, filler, dibutyltin dilaurate, antioxidant, and silicone toughening agent into a container, stir and mix to obtain component A; then add component A and polyurethane prepolymer into a mold, first heat cure at 100-110° C. for 1-2 hours, then heat treat at 110-120° C. for 12-18 hours, and cool to obtain a silicon PU material for an impact-resistant and elastic plastic track.

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