CN115746240A - Preparation process of thermoplastic elastomer material - Google Patents

Abstract

The invention relates to the technical field of elastomers and discloses a preparation process of a thermoplastic elastomer material, wherein under the action of catalysts such as potassium carbonate, the amino group of ethanolamine and chloroacetylated polystyrene are subjected to substitution reaction to obtain ethanol aminated polystyrene, so that active hydroxyethyl is introduced into the side chain of the polystyrene, and then the active hydroxyethyl is used as a crosslinking site to react with an isocyanate-terminated polyurethane prepolymer to obtain the polystyrene-polyurethane composite thermoplastic elastomer material.The crosslinked polyurethane composite thermoplastic elastomer material has better tensile property and impact resistance, the maximum tensile strength reaches 46.5MPa, and the maximum impact strength reaches 17.6kJ/m ² Provides a brand new process for preparing high-performance elastomer materials.

Description

A kind of preparation technology of thermoplastic elastomer material

technical field

The invention relates to the technical field of elastomers, in particular to a preparation process of thermoplastic elastomer materials.

Background technique

Elastomer materials such as polyurethane elastomer, ABS elastomer, polystyrene elastomer, etc. have good deformation resistance and wear resistance, and have important applications in various fields such as injection bonding coating, medical equipment, and mining. , such as Chinese patent 201710404863.9 "A thermoplastic elastomer with PETG secondary injection and its preparation method", using styrene-based block copolymers, copolyester resins and other raw materials to prepare thermoplastic elastomers, applied to PETG secondary In the first shot bonding, it has firm bonding with PETG material, good elasticity and tensile strength, smooth surface and better hand feeling.

Polystyrene block copolymers have important applications in material injection bonding, such as Chinese patent 201911182790.9 "A thermoplastic elastomer material for secondary injection bonding with polyketone materials and its preparation method", which reports the following Polystyrene block copolymer, white oil, thermoplastic polyurethane and other raw materials are used to synthesize thermoplastic elastomer materials for secondary injection bonding with polyketone materials, butadiene in the molecular structure of SBS and thermoplastic polyurethane in the formula The amide bond has good affinity and compatibility with the carbonyl group in the polyketone molecular structure, and can be firmly shot and bonded to the surface of the polyketone material through the secondary injection of the injection molding machine. The present invention aims to synthesize a polyketone with excellent mechanical properties New polystyrene-polyurethane composite elastomer.

Contents of the invention

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.

The object of the present invention is achieved in that a kind of preparation technology of thermoplastic elastomer material, described preparation technology is:

S1. Mix 100 parts by weight of dry polyester polyol with 38-50 parts by weight of diisocyanate and 0.04-0.1 parts by weight of dibutyltin dilaurate; then react at 60-70°C for 2-3 hours to obtain Isocyanate-terminated polyurethane prepolymers;

S2. Stir and mix 100 parts by weight of polyurethane prepolymer and 30-80 parts by weight of ethanol-aminated polystyrene, and pour it into a mold with a preheating temperature of 100-110°C; when the material reaches the gel point, put the material Molding vulcanization at 100-110°C in a vulcanizer for 1-2h, then placing the material in an oven, secondary vulcanization at 100-110°C for 12-24h, and finally vulcanizing at 25-35°C for 48-96h to obtain thermoplastic elastomer material.

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

Preferably, the preparation process of ethanol aminated polystyrene in the S2 is:

S3. Add 100 parts by weight of polystyrene and 80-120 parts by weight of chloroacetyl chloride to the dichloromethane solvent, stir evenly, add 120-150 parts by weight of aluminum chloride, stir at room temperature for 3-6 hours, and then reduce Distilled under pressure, washed with ethanol and dried 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, add the catalyst dropwise, heat up to 70-90° C. for reflux reaction for 6-12 hours, and then distill under reduced pressure. Washing with deionized water and ethanol and drying yields ethanolaminated polystyrene.

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

Preferably, the catalyst in S3 includes potassium carbonate, sodium carbonate, and sodium hydroxide.

Preferably, the catalyst is added dropwise in S3 to adjust the pH of the reaction solution to 5-6.

(3) Beneficial technical effects

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

Under the action of catalysts such as potassium carbonate, the amino group of ethanolamine undergoes a substitution reaction with chloroacetylated polystyrene to obtain ethanol aminated polystyrene, thereby introducing an active hydroxyethyl group into the side chain of polystyrene, and then use it as The cross-linking site reacts with the isocyanate-terminated polyurethane prepolymer to obtain a polystyrene-polyurethane composite thermoplastic elastomer material. The cross-linked 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 , which provides a great opportunity for the preparation of high-performance elastomer materials. The new process, mild reaction conditions, simple and easy-to-operate preparation process are suitable for industrial production; the obtained composite thermoplastic elastomer material has broad application prospects in injection bonding coating, medical equipment, sports equipment, etc.

Detailed ways

Example 1

(1) Add 100 parts by weight of polystyrene and 80 parts by weight of chloroacetyl chloride to the dichloromethane solvent, stir evenly, add 120 parts by weight of aluminum chloride, stir at room temperature for 6 hours, then distill under reduced pressure and wash with ethanol And dried to obtain chloroacetylated polystyrene.

(2) Add 100 parts by weight of chloroacetylated polystyrene and 60 parts by weight of ethanolamine to 1,4-dioxane, stir evenly, add catalyst potassium carbonate dropwise to regulate the pH of the reaction solution to 5, and heat up to 70 ℃ reflux reaction for 12h, and then distilled under reduced pressure, washed with deionized water and ethanol and dried to obtain ethanol aminated polystyrene.

(3) Mix 100 parts by weight of dry polyester polyol with 38 parts by weight of 2,4-toluene diisocyanate and 0.04 parts by weight of dibutyltin dilaurate, and react at 70°C for 2 hours to obtain isocyanate End-capped polyurethane prepolymer.

(4) Stir and mix 100 parts by weight of polyurethane prepolymer and 50 parts by weight of ethanol aminated polystyrene, and pour it into a mold with a preheating temperature of 100 ° C. When the material reaches the gel point, put the material in the vulcanizer Molding vulcanization at 100°C for 2 hours, then placing the material in an oven, secondary vulcanization at 110°C for 18 hours, and finally vulcanization at 35°C for 48 hours to obtain a thermoplastic elastomer material.

Example 2

(1) Add 100 parts by weight of polystyrene and 120 parts by weight of chloroacetyl chloride to the dichloromethane solvent, stir evenly, add 150 parts by weight of aluminum chloride, stir at room temperature for 5 hours, then distill under reduced pressure and wash with ethanol And dried to obtain chloroacetylated polystyrene.

(2) Add 100 parts by weight of chloroacetylated polystyrene and 60 parts by weight of ethanolamine to N,N-dimethylformamide, stir well and add catalyst sodium carbonate dropwise to regulate the pH of the reaction solution to 5, and heat up to Reflux at 80°C for 12 hours, then distill under reduced pressure, wash with deionized water and ethanol and dry to obtain ethanol aminated polystyrene.

(3) Mix 100 parts by weight of dry polyester polyol with 45 parts by weight of isophorone diisocyanate and 0.07 parts by weight of dibutyltin dilaurate, and react at 70°C for 3 hours to obtain isocyanate-sealed Terminal polyurethane prepolymer.

(4) Stir and mix 100 parts by weight of polyurethane prepolymer and 50 parts by weight of ethanol-aminated polystyrene, and pour it into a mold with a preheating temperature of 110 ° C. When the material reaches the gel point, put the material in the vulcanizer Molding vulcanization at 110°C for 2 hours, and then placing the material in an oven for secondary vulcanization at 110°C for 24 hours, and finally vulcanizing at 25°C for 96 hours to obtain a thermoplastic elastomer material.

Example 3

(1) Add 100 parts by weight of polystyrene and 110 parts by weight of chloroacetyl chloride to the dichloromethane solvent, stir evenly, add 140 parts by weight of aluminum chloride, stir at room temperature for 4 hours, then distill under reduced pressure and wash with ethanol And dried to obtain chloroacetylated polystyrene.

(2) Add 100 parts by weight of chloroacetylated polystyrene and 45 parts by weight of ethanolamine to toluene, stir evenly, add dropwise catalyst sodium hydroxide to regulate the pH of the reaction solution to 6, heat up to 80° C. for reflux reaction for 6 hours, and then Distilled under reduced pressure, washed with deionized water and ethanol and dried to obtain ethanol aminated polystyrene.

(3) Mix 100 parts by weight of dry polyester polyol with 50 parts by weight of hexamethylene diisocyanate and 0.1 part by weight of dibutyltin dilaurate, and react at 60°C for 3 hours to obtain isocyanate-sealed Terminal polyurethane prepolymer.

(4) Stir and mix 100 parts by weight of polyurethane prepolymer and 80 parts by weight of ethanol aminated polystyrene, and pour it into a mold with a preheating temperature of 100 ° C. When the material reaches the gel point, put the material in the vulcanizer Molding vulcanization at 110°C for 2 hours, then placing the material in an oven, secondary vulcanization at 110°C for 12 hours, and finally vulcanization at 35°C for 48 hours to obtain a thermoplastic elastomer material.

Example 4

(1) Add 100 parts by weight of polystyrene and 90 parts by weight of chloroacetyl chloride to the dichloromethane solvent, stir evenly, add 120 parts by weight of aluminum chloride, stir at room temperature for 3 hours, then distill under reduced pressure and wash with ethanol And dried to obtain chloroacetylated polystyrene.

(2) Add 100 parts by weight of chloroacetylated polystyrene and 25 parts by weight of ethanolamine to tetrahydrofuran, stir evenly and then dropwise add catalyst potassium carbonate to regulate the pH of the reaction solution to 6, heat up to 70°C for reflux reaction for 6h, then reduce Distilled under high pressure, washed with deionized water and ethanol and dried to obtain ethanol aminated polystyrene.

(3) Mix 100 parts by weight of dry polyester polyol with 40 parts by weight of 4,4-diphenylmethane diisocyanate and 0.1 part by weight of dibutyltin dilaurate, and react at 70°C for 3 hours to obtain Isocyanate terminated polyurethane prepolymer.

(4) Stir and mix 100 parts by weight of polyurethane prepolymer and 30 parts by weight of ethanol aminated polystyrene, and pour it into a mold with a preheating temperature of 100 ° C. When the material reaches the gel point, put the material in the vulcanizer Molding vulcanization at 100°C for 1 hour, then placing the material in an oven, secondary vulcanization at 110°C for 12 hours, and finally vulcanization at 25°C for 72 hours to obtain a thermoplastic elastomer material.

Example 5

(1) Add 100 parts by weight of polystyrene and 100 parts by weight of chloroacetyl chloride to the dichloromethane solvent, stir evenly, add 130 parts by weight of aluminum chloride, stir at room temperature for 6 hours, then distill under reduced pressure and wash with ethanol And dried to obtain chloroacetylated polystyrene.

(2) Add 100 parts by weight of chloroacetylated polystyrene and 40 parts by weight of ethanolamine to 1,4-dioxane, stir evenly, add catalyst potassium carbonate dropwise to regulate the pH of the reaction solution to 6, and heat up to 80 °C for 10 h at reflux, then distilled under reduced pressure, washed with deionized water and ethanol and dried to obtain ethanol aminated polystyrene.

(3) Mix 100 parts by weight of dry polyester polyol with 38 parts by weight of 2,4-toluene diisocyanate and 0.07 parts by weight of dibutyltin dilaurate, and react at 65°C for 3 hours to obtain isocyanate End-capped polyurethane prepolymer.

(4) Stir and mix 100 parts by weight of polyurethane prepolymer and 80 parts by weight of ethanol aminated polystyrene, and pour it into a mold with a preheating temperature of 100 ° C. When the material reaches the gel point, put the material in the vulcanizer Molding vulcanization at 100°C for 2 hours, then placing the material in an oven, secondary vulcanization at 100°C for 18 hours, and finally vulcanization at 35°C for 72 hours to obtain a thermoplastic elastomer material.

Comparative example 1

(1) Mix 100 parts by weight of dry polyester polyol with 45 parts by weight of 2,4-toluene diisocyanate and 0.06 parts by weight of dibutyltin dilaurate, and react at 70°C for 3 hours to obtain isocyanate End-capped polyurethane prepolymer.

(2) Stir and mix 100 parts by weight of polyurethane prepolymer and 30 parts by weight of polystyrene, and pour it into a mold with a preheating temperature of 110 ° C. When the material reaches the gel point, put the material in a vulcanizer for 110 ℃ for 2 hours, and then put the material in an oven for secondary vulcanization at 110 ℃ for 12 hours, and finally at 25 ℃ for 96 hours to obtain a thermoplastic elastomer material.

The impact performance of low temperature resistant high strength thermoplastic elastomer composite materials is measured by impact testing machine, referring to the standard of GB/T 1043.2-2018, the sample size is 80mm×40mm×5mm, and the test speed is 20mm/min.

A tensile testing machine was used to measure the tensile properties of low-temperature resistant high-strength thermoplastic elastomer composites, referring to the standard of GB/T 1040.1-2018, the sample size was 120mm×30mm×4mm, and the tensile rate was 100mm/min.

Tensile strength (MPa) Elongation at break (%) Impact strength (kJ/m²) 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

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

Claims (6)

1. A preparation process of a thermoplastic elastomer material is characterized by comprising the following steps: the preparation process comprises the following steps:

s1, uniformly mixing 100 parts by weight of dried polyester polyol, 38-50 parts by weight of diisocyanate and 0.04-0.1 part by weight of dibutyltin dilaurate; then reacting for 2-3h at 60-70 ℃ to obtain an isocyanate-terminated polyurethane prepolymer;

s2, stirring and mixing 100 parts by weight of polyurethane prepolymer and 30-80 parts by weight of ethanol aminated polystyrene, and pouring the mixture into a mold with a preheating temperature of 100-110 ℃; when the material reaches the gel point, the material is subjected to compression molding vulcanization for 1-2h at 100-110 ℃ in a vulcanizing machine, then the material is placed in an oven, secondary vulcanization is carried out for 12-24h at 100-110 ℃, and finally vulcanization is carried out for 48-96h at 25-35 ℃ to obtain the thermoplastic elastomer material.

2. A process for the preparation of a thermoplastic elastomeric material according to claim 1, characterized in that: the diisocyanate in S1 comprises 2,4-toluene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate and hexamethylene diisocyanate.

3. A process for the preparation of a thermoplastic elastomeric material according to claim 1, characterized in that: the preparation process of the ethanol aminated polystyrene in the S2 comprises the following steps:

s3, adding 100 parts by weight of polystyrene and 80-120 parts by weight of chloroacetyl chloride into a dichloromethane solvent, uniformly stirring, adding 120-150 parts by weight of aluminum chloride, stirring at room temperature for reaction for 3-6 hours, then carrying out reduced pressure distillation, washing and drying to obtain chloroacetylated polystyrene;

s4, adding 100 parts by weight of chloroacetylated polystyrene and 25-60 parts by weight of ethanolamine into a reaction solvent, uniformly stirring, dropwise adding a catalyst, heating to 70-90 ℃, carrying out reflux reaction for 6-12h, then carrying out reduced pressure distillation, washing and drying to obtain the ethanol aminated polystyrene.

4. A process for the preparation of a thermoplastic elastomeric material according to claim 3, characterized in that: the reaction solvent in S3 comprises N, N-dimethylformamide, toluene, tetrahydrofuran and 1,4-dioxane.

5. A process for the preparation of a thermoplastic elastomeric material according to claim 3, characterized in that: and the catalyst in the S3 comprises potassium carbonate, sodium carbonate and sodium hydroxide.

6. A process for the preparation of a thermoplastic elastomeric material according to claim 3, characterized in that: and dropwise adding a catalyst into the S3 to regulate the pH value of the reaction solution to 5-6.