A preparation process of thermoplastic elastomer material

Abstract

The present invention relates to the technical field of elastomers, and discloses a preparation process of a thermoplastic elastomer material. Under the action of a catalyst such as potassium carbonate, the amino group of ethanolamine undergoes a substitution reaction with chloroacetylated polystyrene to obtain ethanolamine polystyrene, thereby introducing an active hydroxyethyl group into the side chain of the polystyrene, which is then used as a crosslinking site to react with an isocyanate-terminated polyurethane prepolymer to obtain a polystyrene-polyurethane composite thermoplastic elastomer material. The crosslinked polyurethane composite thermoplastic elastomer material has better tensile properties and impact resistance, with a maximum tensile strength of 46.5MPa and a maximum impact strength of 17.6kJ / m 2 , providing a new process for the preparation of high-performance elastomer materials.

Description

Technical Field

[0001] The invention relates to the technical field of elastomers, in particular to a preparation process of a thermoplastic elastomer material. Background Art

[0002] Elastomeric materials such as polyurethane elastomers, ABS elastomers, polystyrene elastomers, etc. have excellent deformation resistance, wear resistance and other properties, and have important applications in various fields such as spray bonding, medical equipment, and mining. For example, Chinese patent 201710404863.9 "A thermoplastic elastomer for secondary spray bonding with PETG and its preparation method" uses styrene block copolymers, copolyester resins and other raw materials to prepare thermoplastic elastomers, which are used in PETG secondary spray bonding. It has a firm bond with PETG materials, good elasticity and tensile strength, a smooth surface, and a better feel.

[0003] Polystyrene block copolymers have important applications in material injection coating. For example, Chinese patent 201911182790.9 "A thermoplastic elastomer material for secondary injection bonding with polyketone materials and its preparation method" reports the synthesis of a thermoplastic elastomer material for secondary injection bonding with polyketone materials using polystyrene block copolymers, white oil, thermoplastic polyurethane and other raw materials. The butadiene in the SBS molecular structure and the amide bond in the thermoplastic polyurethane in the formula have good affinity compatibility with the carbonyl group in the polyketone molecular structure. The secondary injection bonding of the injection molding machine can firmly bond to the surface of the polyketone material. The present invention aims to synthesize a new type of polystyrene-polyurethane composite elastomer with excellent mechanical properties. Summary of the invention

[0004] The object of the present invention is to provide a preparation process of a thermoplastic elastomer material, which improves the mechanical properties of the thermoplastic elastomer material.

[0005] The object of the present invention is achieved by: a preparation process of a thermoplastic elastomer material, the preparation process comprising:

[0006] S1. Evenly mix 100 parts by weight of dried polyester polyol, 38-50 parts by weight of diisocyanate, and 0.04-0.1 parts by weight of dibutyltin dilaurate; and then react at 60-70° C. for 2-3 hours to obtain an isocyanate-terminated polyurethane prepolymer;

[0007] S2. 100 parts by weight of polyurethane prepolymer and 30-80 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at 100-110° C.; when the material reaches the gel point, the material is compression-vulcanized in a vulcanizer at 100-110° C. for 1-2 hours, and then the material is placed in an oven and post-vulcanized at 100-110° C. for 12-24 hours, and finally vulcanized at 25-35° C. for 48-96 hours to obtain a thermoplastic elastomer material.

[0008] Preferably, the diisocyanate in S1 includes 2,4-toluene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0009] Preferably, the preparation process of ethanolamine polystyrene in S2 is:

[0010] S3. Add 100 parts by weight of polystyrene and 80-120 parts by weight of chloroacetyl chloride to dichloromethane solvent, stir evenly, then add 120-150 parts by weight of aluminum chloride, stir at room temperature for 3-6 hours, then distill under reduced pressure, wash with ethanol and dry to obtain chloroacetylated polystyrene.

[0011] S4. Add 100 parts by weight of chloroacetylated polystyrene and 25-60 parts by weight of ethanolamine to the reaction solvent, stir evenly and then drop the catalyst, raise the temperature to 70-90°C and reflux for reaction for 6-12 hours, then distill under reduced pressure, wash with deionized water and ethanol and dry to obtain ethanolamine polystyrene.

[0012] Preferably, the reaction solvent in S3 includes N,N-dimethylformamide, toluene, tetrahydrofuran, and 1,4-dioxane.

[0013] Preferably, the catalyst in S4 includes potassium carbonate, sodium carbonate, and sodium hydroxide.

[0014] Preferably, in S4, a catalyst is added dropwise to adjust the pH of the reaction solution to 5-6.

[0015] (III) Beneficial technical effects

[0016] Compared with the prior art, the present invention has the following beneficial technical effects:

[0017] Under the action of a catalyst such as potassium carbonate, the amino group of ethanolamine undergoes a substitution reaction with chloroacetylated polystyrene to obtain ethanolamine polystyrene, thereby introducing an active hydroxyethyl group into the side chain of polystyrene, which is then used as a crosslinking site to react with an isocyanate-terminated polyurethane prepolymer to obtain a polystyrene-polyurethane composite thermoplastic elastomer material. The crosslinked polyurethane composite thermoplastic elastomer material has better tensile properties and impact resistance, with a maximum tensile strength of 46.5MPa and a maximum impact strength of 17.6kJ / m 2 It provides a new process for the preparation of high-performance elastomer materials. The reaction conditions are mild, the preparation process is simple and easy to operate, and it is suitable for industrial production. The obtained composite thermoplastic elastomer material has broad application prospects in spray bonding coating, medical devices, sports equipment, etc. DETAILED DESCRIPTION

[0018] Example 1

[0019] (1) Add 100 parts by weight of polystyrene and 80 parts by weight of chloroacetyl chloride to a dichloromethane solvent, stir well, then add 120 parts by weight of aluminum chloride, stir at room temperature for 6 hours, then distill under reduced pressure, wash with ethanol and dry to obtain chloroacetylated polystyrene.

[0020] (2) Add 100 parts by weight of chloroacetylated polystyrene and 60 parts by weight of ethanolamine to 1,4-dioxane, stir evenly, then dropwise add catalyst potassium carbonate to adjust the pH of the reaction solution to 5, heat to 70° C., reflux for 12 h, then distill under reduced pressure, wash with deionized water and ethanol, and dry to obtain ethanolamine polystyrene.

[0021] (3) 100 parts by weight of dried polyester polyol was mixed evenly with 38 parts by weight of 2,4-toluene diisocyanate and 0.04 parts by weight of dibutyltin dilaurate, and reacted at 70° C. for 2 hours to obtain an isocyanate-terminated polyurethane prepolymer.

[0022] (4) 100 parts by weight of a polyurethane prepolymer and 50 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at 100° C. When the material reaches the gel point, the material is compression-vulcanized in a vulcanizer at 100° C. for 2 h, and then placed in an oven for secondary vulcanization at 110° C. for 18 h, and finally vulcanized at 35° C. for 48 h to obtain a thermoplastic elastomer material.

[0023] Example 2

[0024] (1) Add 100 parts by weight of polystyrene and 120 parts by weight of chloroacetyl chloride to a dichloromethane solvent, stir well, then add 150 parts by weight of aluminum chloride, stir at room temperature for 5 hours, then distill under reduced pressure, wash with ethanol and dry to obtain chloroacetylated polystyrene.

[0025] (2) Add 100 parts by weight of chloroacetylated polystyrene and 60 parts by weight of ethanolamine to N,N-dimethylformamide, stir evenly, then dropwise add catalyst sodium carbonate to adjust the pH of the reaction solution to 5, heat to 80° C., reflux for 12 h, then distill under reduced pressure, wash with deionized water and ethanol, and dry to obtain ethanolamine polystyrene.

[0026] (3) 100 parts by weight of dried polyester polyol was mixed evenly with 45 parts by weight of isophorone diisocyanate and 0.07 parts by weight of dibutyltin dilaurate, and reacted at 70° C. for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer.

[0027] (4) 100 parts by weight of a polyurethane prepolymer and 50 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at 110° C. When the material reaches the gel point, the material is compression-vulcanized in a vulcanizer at 110° C. for 2 h, and then placed in an oven for secondary vulcanization at 110° C. for 24 h, and finally vulcanized at 25° C. for 96 h to obtain a thermoplastic elastomer material.

[0028] Example 3

[0029] (1) Add 100 parts by weight of polystyrene and 110 parts by weight of chloroacetyl chloride to a dichloromethane solvent, stir well, then add 140 parts by weight of aluminum chloride, stir at room temperature for 4 hours, then distill under reduced pressure, wash with ethanol and dry to obtain chloroacetylated polystyrene.

[0030] (2) Add 100 parts by weight of chloroacetylated polystyrene and 45 parts by weight of ethanolamine to toluene, stir evenly, then dropwise add catalyst sodium hydroxide to adjust the pH of the reaction solution to 6, heat to 80° C., reflux for 6 h, and then distill under reduced pressure, wash with deionized water and ethanol, and dry to obtain ethanolamine polystyrene.

[0031] (3) 100 parts by weight of dried polyester polyol was mixed evenly with 50 parts by weight of hexamethylene diisocyanate and 0.1 parts by weight of dibutyltin dilaurate, and reacted at 60° C. for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer.

[0032] (4) 100 parts by weight of a polyurethane prepolymer and 80 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at 100° C. When the material reaches the gel point, the material is compression-vulcanized at 110° C. in a vulcanizer for 2 h, and then placed in an oven for secondary vulcanization at 110° C. for 12 h, and finally vulcanized at 35° C. for 48 h to obtain a thermoplastic elastomer material.

[0033] Example 4

[0034] (1) Add 100 parts by weight of polystyrene and 90 parts by weight of chloroacetyl chloride to a dichloromethane solvent, stir well, then add 120 parts by weight of aluminum chloride, stir at room temperature for 3 hours, then distill under reduced pressure, wash with ethanol and dry to obtain chloroacetylated polystyrene.

[0035] (2) Add 100 parts by weight of chloroacetylated polystyrene and 25 parts by weight of ethanolamine to tetrahydrofuran, stir evenly, then dropwise add catalyst potassium carbonate to adjust the pH of the reaction solution to 6, heat to 70° C., reflux for 6 h, then distill under reduced pressure, wash with deionized water and ethanol, and dry to obtain ethanolamine polystyrene.

[0036] (3) 100 parts by weight of dried polyester polyol was mixed evenly with 40 parts by weight of 4,4-diphenylmethane diisocyanate and 0.1 parts by weight of dibutyltin dilaurate, and reacted at 70° C. for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer.

[0037] (4) 100 parts by weight of a polyurethane prepolymer and 30 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at 100° C. When the material reaches the gel point, the material is compression-vulcanized in a vulcanizer at 100° C. for 1 hour, and then the material is placed in an oven and post-vulcanized at 110° C. for 12 hours, and finally vulcanized at 25° C. for 72 hours to obtain a thermoplastic elastomer material.

[0038] Example 5

[0039] (1) Add 100 parts by weight of polystyrene and 100 parts by weight of chloroacetyl chloride to a dichloromethane solvent, stir well, then add 130 parts by weight of aluminum chloride, stir at room temperature for 6 hours, then distill under reduced pressure, wash with ethanol and dry to obtain chloroacetylated polystyrene.

[0040] (2) Add 100 parts by weight of chloroacetylated polystyrene and 40 parts by weight of ethanolamine to 1,4-dioxane, stir evenly, then dropwise add catalyst potassium carbonate to adjust the pH of the reaction solution to 6, heat to 80° C., reflux for 10 h, then distill under reduced pressure, wash with deionized water and ethanol, and dry to obtain ethanolamine polystyrene.

[0041] (3) 100 parts by weight of dried polyester polyol was mixed evenly with 38 parts by weight of 2,4-toluene diisocyanate and 0.07 parts by weight of dibutyltin dilaurate, and reacted at 65° C. for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer.

[0042] (4) 100 parts by weight of a polyurethane prepolymer and 80 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at 100° C. When the material reaches the gel point, the material is compression-vulcanized in a vulcanizer at 100° C. for 2 h, and then placed in an oven for secondary vulcanization at 100° C. for 18 h, and finally vulcanized at 35° C. for 72 h to obtain a thermoplastic elastomer material.

[0043] Comparative Example 1

[0044] (1) 100 parts by weight of dried polyester polyol was mixed evenly with 45 parts by weight of 2,4-toluene diisocyanate and 0.06 parts by weight of dibutyltin dilaurate, and reacted at 70° C. for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer.

[0045] (2) 100 parts by weight of a polyurethane prepolymer and 30 parts by weight of polystyrene are stirred and mixed, and poured into a mold preheated at 110° C. When the material reaches the gel point, the material is compression-vulcanized in a vulcanizer at 110° C. for 2 h, and then placed in an oven for secondary vulcanization at 110° C. for 12 h, and finally vulcanized at 25° C. for 96 h to obtain a thermoplastic elastomer material.

[0046] The impact testing machine was used to measure the impact properties of the low-temperature resistant and high-strength thermoplastic elastomer composite material. The standard of GB / T 1043.2-2018 was referred to. The specimen was 80mm×40mm×5mm and the test rate was 20mm / min.

[0047] The tensile properties of the low-temperature-resistant high-strength thermoplastic elastomer composite material were determined by a tensile testing machine, referring to the standard GB / T 1040.1-2018. The sample was 120mm×30mm×4mm and the tensile rate was 100mm / min.

[0048] Tensile strength(MPa) Elongation at break (%) <![CDATA[Impact strength (kJ / m 2 )]]> Example 1 41.9 536.0 12.4 Example 2 36.2 594.2 16.0 Example 3 45.7 506.7 17.6 Example 4 39.3 471.9 13.1 Example 5 46.5 560.7 15.4 Comparative Example 1 27.6 461.7 9.7

[0049] The tensile strength and elongation at break of the low-temperature-resistant high-strength thermoplastic elastomer composite material are 46.5MPa and 594.2% respectively, and the impact strength is 17.6kJ / m 2 .

Claims

1. A process for preparing a thermoplastic elastomer material, characterized in that: The preparation process is: S1. Evenly mix 100 parts by weight of dried polyester polyol, 38-50 parts by weight of diisocyanate, and 0.04-0.1 parts by weight of dibutyltin dilaurate; and then react at 60-70° C. for 2-3 hours to obtain an isocyanate-terminated polyurethane prepolymer; S2, 100 parts by weight of polyurethane prepolymer and 30-80 parts by weight of ethanolamine polystyrene are stirred and mixed, and poured into a mold preheated at a temperature of 100-110° C.; when the material reaches the gel point, the material is molded and vulcanized in a vulcanizer at 100-110° C. for 1-2 hours, and then the material is placed in an oven and post-vulcanized at 100-110° C. for 12-24 hours, and finally vulcanized at 25-35° C. for 48-96 hours to obtain a thermoplastic elastomer material; Wherein, the preparation process of ethanolamine polystyrene in S2 is: S3, add 100 parts by weight of polystyrene and 80-120 parts by weight of chloroacetyl chloride to dichloromethane solvent, stir evenly, add 120-150 parts by weight of aluminum chloride, stir at room temperature for 3-6 hours, then distill under reduced pressure, wash and dry to obtain chloroacetylated polystyrene; S4. Add 100 parts by weight of chloroacetylated polystyrene and 25-60 parts by weight of ethanolamine to the reaction solvent, stir evenly and then drop the catalyst, raise the temperature to 70-90°C and reflux for reaction for 6-12 hours, then distill under reduced pressure, wash and dry to obtain ethanolamine polystyrene.

2. The process for preparing a thermoplastic elastomer material according to claim 1, characterized in that: The diisocyanate in S1 includes 2,4-toluene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

3. The process for preparing a thermoplastic elastomer material according to claim 1, characterized in that: The reaction solvent in S3 includes N,N-dimethylformamide, toluene, tetrahydrofuran, and 1,4-dioxane.

4. The process for preparing a thermoplastic elastomer material according to claim 1, characterized in that: The catalyst added dropwise in S4 includes potassium carbonate, sodium carbonate, and sodium hydroxide.

5. The process for preparing a thermoplastic elastomer material according to claim 1, characterized in that: In the step S4, a catalyst is added dropwise to adjust the pH of the reaction solution to 5-6.