A kind of impact-resistant elastic silicon PU material for plastic runway and its preparation method

Abstract

The present invention relates to the field of polyurethane plastic technology, and discloses a kind of impact-resistant elastic plastic runway silicon PU material and preparation method thereof, the raw material of the PU material of the present invention includes component A, 100 parts of polyether polyols, 25 40 parts of fillers, 10 30 parts of organosilicon toughening agents; component B, 100 parts of polyether polyols, 68 75 parts of diphenylmethane 4,4 '-diisocyanates. There is good compatibility between the organosilicon toughening agent of the present invention and polyurethane, can be evenly dispersed in the polyurethane matrix, containing flexible siloxane structure, plays a good toughening effect on polyurethane, significantly improves the impact strength, flexural strength, wear resistance of PU materials. And the organosilicon toughening agent contains a diazinone structure with high temperature resistance, is added to polyurethane, and can improve the thermal decomposition temperature and heat resistance of the material.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane plastics, and in particular to a silicon PU material for an impact-resistant and elastic plastic runway and a preparation method thereof. Background Art

[0002] Plastic tracks are a common sports facility, primarily made of polyvinyl chloride, polyurethane, and rubber. Polyurethane is non-toxic and odorless, highly elastic, and exhibits excellent low-temperature and aging resistance. It can be made into elastomers, foams, and plastics, finding widespread application in industries such as plastic tracks, sporting goods, electronics, and the automotive industry. Improving the impact resistance, heat resistance, and wear resistance of polyurethane and its elastomers could enhance their practical applications in materials like plastic tracks.

[0003] Silicones have excellent toughness, wear resistance, chemical resistance, and corrosion resistance, and are therefore important in polymer materials such as polyurethane, polyethylene, and rubber. Chinese patent CN119039766B discloses an environmentally friendly, highly elastic polyurethane-modified acrylic runway adhesive and its preparation method. Using acrylate compounds, methyltrimethoxysilane, octamethylcyclotetrasiloxane, and an aqueous polyurethane emulsion as raw materials, the polyurethane-modified acrylic runway adhesive exhibits advantages such as high elasticity and excellent tensile properties. However, the polyurethane runway adhesive disclosed in this patent exhibits a low thermal decomposition weight loss temperature and does not improve the impact strength and flexural strength of the polyurethane. Summary of the Invention

[0004] The invention solves the problem that the polyurethane material used for the plastic runway has poor elasticity, impact resistance and wear resistance.

[0005] The technical solution of the present invention is a silicon PU material for an impact-resistant and elastic plastic track. The raw materials of the silicon PU material include component A and component B by weight.

[0006] 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.

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

[0008] Furthermore, a method for preparing a silicon PU material is characterized in that the preparation method is:

[0009] (1) Nitrogen is introduced into the reactor, and the raw materials of component B, polyether polyol and diphenylmethane-4,4'-diisocyanate, are added, heated to 70-75°C, and reacted for 2-3 hours to obtain a polyurethane prepolymer.

[0010] (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.

[0011] Furthermore, the polyether polyol is polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

[0012] Furthermore, the filler is montmorillonite, talc or calcium carbonate powder.

[0013] Furthermore, the preparation method of acrylated phthalazinone is as follows: adding a solvent, 100 parts (by weight) of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 130-144 parts of isocyanoethyl methacrylate, and 0.24-0.36 parts of dibutyltin dilaurate to a reaction vessel, introducing nitrogen, reacting at 60-70°C for 1-1.5 hours, distilling under reduced pressure, washing the product with n-hexane, and then recrystallizing it with ethanol to obtain acrylated phthalazinone. The reaction formula is:

[0014]

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

[0016] Furthermore, the preparation method of the organosilicon toughening agent is as follows: tetrahydrofuran, 100 parts (by weight) of phthalazinone acrylate, 24-28 parts of 1,1,3,3-tetramethyldisiloxane, and an isopropanol solution containing 0.9-1.3 parts of chloroplatinic acid are added to a reaction vessel, nitrogen is introduced, the mixture is heated to 60-70°C, condensed and refluxed for 6-10 hours, and the mixture is distilled under reduced pressure, the product is washed with ethanol, and dried to obtain the organosilicon toughening agent. The reaction formula is:

[0017]

[0018] The technical effect of the present invention is that the present invention utilizes a hydrosilylation polymerization reaction between acrylate-based phthalazinone and 1,1,3,3-tetramethyldisiloxane to produce an organosilicon toughening agent containing a phthalazinone structure. This is then combined with fillers such as polyether polyol and montmorillonite to form the A component of the polyurethane. The B component is formed by reacting the polyether polyol with diphenylmethane-4,4'-diisocyanate to produce an isocyanate-terminated prepolymer, which is then thermally cured to produce the silicone PU material for plastic tracks.

[0019] The organosilicon toughening agent of the present invention contains the same carbamate groups as polyurethane, similar in polarity to PU, and also contains urea groups, which can form stable hydrogen bonding interactions with the polyurethane. This ensures excellent compatibility between the organosilicon toughening agent and the polyurethane, allowing for uniform dispersion within the polyurethane matrix. The organosilicon toughening agent also contains a flexible siloxane structure, which effectively toughens the polyurethane, significantly improving the impact and flexural strength of the PU material, while reducing the wear volume of the PU material and enhancing its wear resistance. Furthermore, the organosilicon toughening agent contains a high-temperature-resistant phthalazinone structure, which, when added to the polyurethane, can increase the thermal decomposition temperature and heat resistance of the material. DETAILED DESCRIPTION

[0020] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0021] Example 1:

[0022] (1) 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 were added to a reaction vessel, nitrogen was introduced, and the mixture was reacted at 65° C. for 1.5 h. The mixture was distilled under reduced pressure, the product was washed with n-hexane, and then recrystallized with ethanol to obtain acrylated phthalazin-1-one.

[0023] (2) Add 250 mL of tetrahydrofuran, 10 g of acrylated phthalazinone, 2.4 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.13 g of chloroplatinic acid into a reaction vessel, introduce nitrogen, heat to 60° C., condense and reflux for 10 h, distill under reduced pressure, wash the product with ethanol, and dry to obtain an organosilicon toughening agent.

[0024] (3) Nitrogen was introduced into the reaction kettle, and 100 g of polytetramethylene ether glycol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in the raw materials of component B were added, and the mixture was heated to 75° C. and reacted for 2 h to obtain a polyurethane prepolymer.

[0025] (4) Add 100g of polytetramethylene ether glycol 1000, 40g of filler calcium carbonate powder, 1.5g of dibutyltin dilaurate, 1.8g of antioxidant 1010, and 10g of 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 110°C for 1h, then heat treat at 120°C for 12h, and cool to obtain impact-resistant and elastic silicone PU material for plastic track.

[0026] Example 2:

[0027] (1) 100 mL of tetrahydrofuran, 5 g of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 6.5 g of isocyanoethyl methacrylate, and 0.018 g of dibutyltin dilaurate were added to a reaction vessel, nitrogen was introduced, and the mixture was refluxed at 60° C. for 1.5 h. The mixture was distilled under reduced pressure, the product was washed with n-hexane, and then recrystallized with ethanol to obtain acrylated phthalazin-1-one.

[0028] (2) 300 mL of tetrahydrofuran, 10 g (18.25 mmol) of phthalazinone acrylate, 2.8 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.13 g of chloroplatinic acid were added to a reaction vessel, nitrogen was introduced, the mixture was heated to 60° C., condensed and refluxed for 10 h, and the mixture was distilled under reduced pressure. The product was washed with ethanol and dried to obtain an organosilicon toughening agent.

[0029] (3) Nitrogen was introduced into the reactor, and 100 g of polyethylene glycol 1000 (component B) and 75 g of diphenylmethane-4,4'-diisocyanate were added. The reaction was heated to 70° C. and reacted for 3 h to obtain a polyurethane prepolymer.

[0030] (4) Add 100g of polyethylene glycol 1000, 25g of filler montmorillonite, 2g of dibutyltin dilaurate, 1.3g of antioxidant 1010, and 15g of 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°C for 2h, then heat treat at 110°C for 18h, and cool to obtain impact-resistant and elastic silicone PU material for plastic track.

[0031] Example 3:

[0032] (1) 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 were added to a reaction vessel, nitrogen was introduced, and the mixture was reacted at 70° C. for 1 h. The mixture was distilled under reduced pressure, the product was washed with n-hexane, and then recrystallized with ethanol to obtain acrylated phthalazin-1-one.

[0033] (2) Add 300 mL of tetrahydrofuran, 10 g of acrylated phthalazinone, 2.6 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.012 g of chloroplatinic acid into a reaction vessel, introduce nitrogen, heat to 70° C., condense and reflux for 6 h, distill under reduced pressure, wash the product with ethanol, and dry to obtain an organosilicon toughening agent.

[0034] (3) Nitrogen was introduced into the reactor, and 100 g of polypropylene glycol 1000 (component B) and 68 g of diphenylmethane-4,4'-diisocyanate were added. The reaction was heated to 75° C. and reacted for 2 h to obtain a polyurethane prepolymer.

[0035] (4) Add 100g of polypropylene glycol 1000, 28g of filler talc powder, 1.2g of dibutyltin dilaurate, 1g of antioxidant 1010, and 20g of 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°C for 2h, then heat treat at 120°C for 12h, and cool to obtain impact-resistant and elastic silicone PU material for plastic runway.

[0036] Example 4:

[0037] (1) Add 100 g of polytetramethylene glycol 1000, 40 g of filler calcium carbonate powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 25 g of silicone toughening agent (prepared in the same manner as in Example 1) into a container, stir and mix to obtain component A; then add component A and a polyurethane prepolymer (prepared in the same manner as in Example 1) into a mold, first heat cure at 110 ° C for 1 h, then heat treat at 120 ° C for 12 h, and cool to obtain a silicon PU material for a plastic runway with impact resistance and elasticity.

[0038] Example 5:

[0039] (1) Add 100 g of polytetramethylene ether glycol 1000, 40 g of filler calcium carbonate powder, 1.5 g of dibutyltin dilaurate, 1.8 g of antioxidant 1010, and 30 g of silicone toughening agent (prepared in the same manner as in Example 1) into a container, stir and mix to obtain component A; then add component A and a polyurethane prepolymer (prepared in the same manner as in Example 1) into a mold, first heat cure at 110° C. for 1 h, then heat treat at 120° C. for 12 h, and cool to obtain a silicon PU material for a plastic runway with impact resistance and elasticity.

[0040] Comparative Example 1:

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

[0042] (2) Add 100 g of polytetramethylene glycol 1000, 40 g of filler calcium carbonate powder, 1.5 g of dibutyltin dilaurate, and 1.8 g of antioxidant 1010 into a container, stir and mix to obtain component A; then add component A and polyurethane prepolymer into a mold, first heat cure at 110°C for 1 hour, then heat treat at 120°C for 12 hours, and cool to obtain silicon PU material for plastic track.

[0043] Comparative Example 2:

[0044] (1) Add 250 mL of tetrahydrofuran, 3.98 g (18.25 mmol) of butyl terephthalate (structural formula: CAS No. 6729-79-9), 2.4 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.13 g of chloroplatinic acid were introduced with nitrogen, heated to 60°C, and refluxed under condensation for 10 hours. The mixture was distilled under reduced pressure, washed with ethanol, and dried to obtain an organosilicon toughening agent.

[0045] (2) Nitrogen was introduced into the reaction kettle, and 100 g of polytetramethylene ether glycol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in the raw materials of component B were added, and the mixture was heated to 75° C. and reacted for 2 h to obtain a polyurethane prepolymer.

[0046] (3) Add 100g of polytetramethylene ether glycol 1000, 40g of filler calcium carbonate powder, 1.5g of dibutyltin dilaurate, 1.8g of antioxidant 1010, and 10g of 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 110°C for 1h, then heat treat at 120°C for 12h, and cool to obtain silicon PU material for plastic track.

[0047] Comparative Example 3:

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

[0049]

[0050] (2) Add 250 mL of tetrahydrofuran, 7.65 g (18.25 mmol) of an acrylate compound, 2.4 g of 1,1,3,3-tetramethyldisiloxane, and 6 mL of an isopropanol solution containing 0.13 g of chloroplatinic acid into a reaction vessel, introduce nitrogen, heat to 60°C, condense and reflux for 10 h, distill under reduced pressure, wash the product with ethanol, and dry to obtain an organosilicon toughening agent.

[0051] (3) Nitrogen was introduced into the reaction kettle, and 100 g of polytetramethylene ether glycol 1000 and 72 g of diphenylmethane-4,4'-diisocyanate in the raw materials of component B were added, and the mixture was heated to 75° C. and reacted for 2 h to obtain a polyurethane prepolymer.

[0052] (4) Add 100g of polytetramethylene ether glycol 1000, 40g of filler calcium carbonate powder, 1.5g of dibutyltin dilaurate, 1.8g of antioxidant 1010, and 10g of 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 110°C for 1h, then heat treat at 120°C for 12h, and cool to obtain silicon PU material for plastic track.

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

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

[0055] Table 1 PU material performance test

[0056]

[0057]

[0058] As can be seen from the table above, the PU materials of Examples 1-5 incorporate an organosilicon toughening agent. This agent contains the same carbamate group (-O-CO=NH) as the polyurethane, similar in polarity to the PU, and also contains urea groups (N-CO-NH), which form stable hydrogen bonding interactions with the polyurethane. This results in excellent compatibility between the organosilicon toughening agent and the polyurethane, allowing for uniform dispersion within the polyurethane matrix. The organosilicon toughening agent contains a flexible siloxane structure, which significantly toughens the polyurethane, significantly improving the impact and flexural strength of the PU material, while also reducing the wear volume and enhancing its wear resistance. Furthermore, the organosilicon toughening agent contains a high-temperature-resistant phthalazinone structure, which, when added to the polyurethane, improves the material's heat resistance and results in a higher thermal decomposition temperature.

[0059] Comparative Example 1 does not add organic silicon toughening agent, the impact strength and bending strength of polyurethane PU material are low, the wear volume is large, and the wear resistance is poor. 5％ and T max Low, poor heat resistance.

[0060] Comparative Example 2 uses butyl terephthalate as raw material to prepare an organosilicon toughening agent that does not contain carbamate groups and urea groups, has poor compatibility with polyurethane, has a poor toughening effect, and does not contain a diazonitrile structure with high-temperature resistance. The thermal decomposition temperature of the PU material is low and the heat resistance is poor.

[0061] The acrylate-based compound and the organosilicon toughening agent prepared in Comparative Example 3 do not contain a diazinone 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 illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection 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 the structural formula 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, washed with ethanol, and dried to obtain an organosilicon toughening agent.

2. The impact-resistant and elastic silicon PU material for plastic runway according to claim 1, wherein 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, talc or calcium carbonate powder.

4. The impact-resistant and elastic silicon PU material for plastic track 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 track according to claim 1, characterized in that: By weight, the amount of the acrylated 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 track 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 a plastic runway according to claim 6, wherein the solvent is tetrahydrofuran or toluene.

8. The impact-resistant and elastic silicon PU material for plastic track according to claim 6, characterized in that: By weight, the amount of 4-(4-hydroxyphenyl)-2,3-phthalazin-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 a plastic track according to any one of claims 1 to 8, characterized in that: The preparation method is: (1) nitrogen was introduced into the reaction kettle, and polyether polyol (B) and diphenylmethane-4,4'-diisocyanate (DPI) were added, and the mixture was heated to 70-75° C. and reacted for 2-3 hours to obtain 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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