A preparation method of high temperature resistant TPE thermoplastic elastomer material

Abstract

The invention relates to the technical field of elastomer materials and discloses a method for preparing a high-temperature resistant TPE thermoplastic elastomer material. The method comprises the following steps: blending hydrogenated styrene-butadiene-styrene block copolymer (SEBS), polypropylene, alkane naphthalene polystyrene grafted graphene and an antioxidant, and then melt-extruding and granulating the mixture in a twin-screw extruder to obtain the high-temperature resistant TPE thermoplastic elastomer material. The method introduces a polystyrene molecular chain containing a long alkyl chain and a naphthalene ring structure on the surface of graphene, so that the graphene can be better dispersed in an elastomer material composed of SEBS and polypropylene, significantly improving the tensile strength, elongation at break, hardness and thermal weight loss temperature of the material, and exhibiting excellent mechanical properties and high-temperature resistance.

Description

Technical Field

[0001] The invention relates to the technical field of elastomer materials, and in particular to a method for preparing a high-temperature resistant TPE thermoplastic elastomer material. Background Art

[0002] TPE thermoplastic elastomers mainly include styrenes, olefins, dienes, polyurethanes, etc., which have the high elasticity and aging resistance of cross-linked vulcanized rubber, and the convenient processing of plastics. They are widely used in the fields of shoemaking industry, adhesives, wires and cables, hoses and tapes. According to the different preparation methods, thermoplastic elastomers can be divided into chemically synthesized thermoplastic elastomers and rubber-plastic blended thermoplastic elastomers. The patent with publication number CN118307926A discloses a weather-resistant and anti-explosion material for plastic plants and its preparation method. SEBS, polypropylene, modified filler, thermoplastic polyurethane elastomer, carboxylated carbon nanotubes, graphene oxide, carboxymethyl chitosan and acrolein are used as raw materials. The prepared weather-resistant and anti-explosion material has good mechanical properties and stability. Compared with the invention, the present invention grafts polystyrene molecular chains containing alkyl long chains and naphthalene ring structures on the surface of graphene oxide, so that the SEBS / polypropylene TPE thermoplastic elastomer material has higher mechanical properties and high temperature resistance. Summary of the invention

[0003] (I) Technical problems to be solved: In view of the deficiencies in the prior art, the present invention provides a TPE thermoplastic elastomer material with good mechanical properties and strong high temperature resistance.

[0004] (II) Technical solution: A method for preparing a high temperature resistant TPE thermoplastic elastomer material:

[0005] (1) Add toluene and acryloyl chloride grafted graphene into a flask, stir and disperse, then add the structural formula The alkane naphthalene styrene monomer, n is any integer between 9 and 15; after stirring and dissolving, nitrogen is introduced, azobisisobutyronitrile is added, the mixture is stirred for reaction, filtered, and then washed with dichloromethane and ethanol in sequence, and dried to obtain alkane naphthalene polystyrene grafted graphene.

[0006] (2) adding hydrogenated styrene-butadiene-styrene block copolymer SEBS, polypropylene, alkane naphthalene polystyrene grafted graphene, and antioxidant into a mixer, and adding the materials into a twin-screw extruder after blending, and melt extruding, with a screw temperature of 195-210° C. and a screw speed of 300-400 r / min; and granulating to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0007] Preferably, the reaction temperature in (1) is 70-85°C and the reaction time is 12-18h.

[0008] Preferably, in (1), the mass ratio of acryloyl chloride grafted graphene, alkane naphthalene styrene monomer, and azobisisobutyronitrile is 100:(150-400):(0.87-2.34).

[0009] Preferably, in (2), the mass ratio of hydrogenated styrene-butadiene-styrene block copolymer SEBS, polypropylene, and alkane naphthalene polystyrene grafted graphene is (60-90):(10-40):(1-5).

[0010] Preferably, the preparation method of alkane naphthalene styrene monomer is:

[0011] S1. Add ethanol, 4-chloromethylstyrene, 1-naphthylamine and sodium carbonate in a mass ratio of 100:(93-122):(0.72-0.86) to a flask, add water, heat to 50-65°C, stir to react for 6-10h, concentrate under reduced pressure, add water to dilute, add ethyl acetate to extract, dry the ethyl acetate extract over anhydrous sodium sulfate, filter, heat the filtrate to evaporate, cool in an ice-water bath for recrystallization, and obtain an intermediate.

[0012] S2. In an ice-water bath, add dichloromethane, the intermediate, the alkyl acyl chloride compound, and triethylamine in a mass ratio of 100:(74-106):(38-46) to a flask, then stir and react at room temperature for 12-15 hours, distill under reduced pressure, wash with water, and dissolve the dried product in dichloromethane, heat to volatilize, cool in an ice-water bath to recrystallize, and obtain an alkane naphthalene styrene monomer. The reaction formula is:

[0013]

[0014] Preferably, the structural formula of the alkyl acyl chloride compound is n is any integer between 9 and 15.

[0015] Preferably, the preparation method of acryloyl chloride grafted graphene is: add N,N-dimethylformamide, graphene oxide, and triethylamine into a flask, introduce nitrogen after ultrasonic dispersion, add acryloyl chloride in an ice bath, stir for reaction, filter, wash with ethanol, and dry to obtain acryloyl chloride grafted graphene.

[0016] (III) Technical effect: The present invention uses acryloyl chloride to react with the hydroxyl groups on the surface of graphene oxide to obtain acryloyl chloride grafted graphene containing alkenyl groups on the surface. 4-chloromethylstyrene, 1-naphthylamine and alkyl acyl chloride compounds are used as raw materials to prepare alkane naphthalene styrene monomers, which then undergo in-situ graft polymerization reaction with the alkenyl groups on the surface of acryloyl chloride grafted graphene to obtain alkane naphthalene polystyrene grafted graphene, thereby introducing polystyrene molecular chains containing naphthalene ring structures on the graphene surface. The compatibility between the polystyrene molecular chain and the hydrogenated styrene-butadiene-styrene block copolymer SEBS is better, and the naphthalene ring structure has a higher thermal decomposition temperature and thermal stability. At the same time, the introduced alkyl long chain has structural similarity with polypropylene, which can improve the compatibility between graphene and polypropylene, so that the graphene can be better dispersed in the elastomeric material composed of SEBS and polypropylene, significantly improving the tensile strength, elongation at break, hardness and thermal weight loss temperature of the material, showing excellent mechanical properties and high temperature resistance. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in conjunction with the following embodiments, but the embodiments are not all embodiments.

[0018] Example 1

[0019] (1) Add 70 mL of N,N-dimethylformamide, 1 g of graphene oxide, and 1.8 g of triethylamine into a flask, introduce nitrogen after ultrasonic dispersion, add 1.6 g of acryloyl chloride in an ice bath, stir and react for 24 h, filter, wash with ethanol, and dry to obtain acryloyl chloride-grafted graphene.

[0020] (2) Add 30 mL of ethanol, 2 g of 4-chloromethylstyrene, 1.86 g of 1-naphthylamine, and 1.72 g of sodium carbonate to a flask, add 6 mL of water, heat to 50° C., stir and react for 10 h, concentrate under reduced pressure, add water to dilute, add ethyl acetate to extract, dry the ethyl acetate extract over anhydrous sodium sulfate, filter, heat the filtrate to evaporate, cool in an ice-water bath and recrystallize to obtain an intermediate.

[0021] (3) In an ice-water bath, 65 mL of dichloromethane, 5 g of the intermediate, 4.7 g of dodecanoyl chloride, and 2.3 g of triethylamine were added to a flask, and then stirred for reaction at room temperature for 12 h, distilled under reduced pressure, washed with water, and the product was dissolved in dichloromethane after drying, heated for volatilization, cooled in an ice-water bath for recrystallization, and an alkane naphthalene styrene monomer was obtained.

[0022] (4) Add 100 mL of toluene and 1 g of acryloyl chloride grafted graphene into a flask, stir and disperse, then add 1.5 g of alkane naphthalene styrene monomer, stir and dissolve, then introduce nitrogen, add 8.7 mg of azobisisobutyronitrile, heat to 75° C. and stir to react for 12 h, filter, wash with dichloromethane and ethanol in turn, and dry to obtain alkane naphthalene polystyrene grafted graphene.

[0023] (5) Add 900 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 100 g of polypropylene, 10 g of alkane naphthalene polystyrene grafted graphene, and 0.3 g of antioxidant 1010 into a high-speed mixer, add the materials into a twin-screw extruder after blending, melt extrude, the screw temperature is 195° C., and the screw speed is 350 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0024] Example 2

[0025] (1) Add 20 mL of ethanol, 2 g of 4-chloromethylstyrene, 2.44 g of 1-naphthylamine, and 1.44 g of sodium carbonate to a flask, add 4 mL of water, heat to 65° C., stir to react for 6 h, concentrate under reduced pressure, add water to dilute, add ethyl acetate to extract, dry the ethyl acetate extract over anhydrous sodium sulfate, filter, heat the filtrate to evaporate, cool in an ice-water bath for recrystallization, and obtain an intermediate.

[0026] (2) In an ice-water bath, 60 mL of dichloromethane, 5 g of the intermediate, 3.7 g of decanoyl chloride, and 2 g of triethylamine were added to a flask, followed by stirring and reacting for 12 h at room temperature, distillation under reduced pressure, washing with water, and drying. The product was dissolved in dichloromethane, heated for volatilization, and cooled in an ice-water bath for recrystallization to obtain an alkane naphthalene styrene monomer.

[0027] (3) 120 mL of toluene and 1 g of acryloyl chloride grafted graphene (prepared in Example 1) were added to a flask, and 3.2 g of alkane naphthalene styrene monomer was added after stirring and dispersing. After stirring and dissolving, nitrogen was introduced, and 18.3 mg of azobisisobutyronitrile was added. The mixture was heated to 70° C. and stirred for reaction for 18 h. After filtering, the mixture was washed with dichloromethane and ethanol in turn, and dried to obtain alkane naphthalene polystyrene grafted graphene.

[0028] (4) Add 800 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 200 g of polypropylene, 20 g of alkane naphthalene polystyrene grafted graphene, and 0.3 g of antioxidant 1010 into a high-speed mixer, add the materials into a twin-screw extruder after blending, melt extrude, the screw temperature is 200° C., and the screw speed is 400 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0029] Example 3

[0030] (1) In an ice-water bath, 70 mL of dichloromethane, 5 g of the intermediate (prepared in Example 1), 5.3 g of palmitoyl chloride, and 1.9 g of triethylamine were added to a flask, followed by stirring and reacting at room temperature for 15 h, distilled under reduced pressure, washed with water, and dried. The product was dissolved in dichloromethane, heated for volatilization, cooled in an ice-water bath for recrystallization, and an alkane naphthalene styrene monomer was obtained.

[0031] (2) 120 mL of toluene and 1 g of acryloyl chloride grafted graphene (prepared in Example 1) were added to a flask, and after stirring and dispersing, 4 g of alkane naphthalene styrene monomer was added, and after stirring and dissolving, nitrogen was introduced, and 23.4 mg of azobisisobutyronitrile was added. The mixture was heated to 85° C. and stirred for reaction for 12 h. After filtering, the mixture was washed with dichloromethane and ethanol in turn, and dried to obtain alkane naphthalene polystyrene grafted graphene.

[0032] (3) Add 700 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 300 g of polypropylene, 35 g of alkane naphthalene polystyrene grafted graphene, and 0.3 g of antioxidant 1010 to a high-speed mixer, add the materials to a twin-screw extruder after blending, melt extrude, the screw temperature is 210° C., and the screw speed is 300 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0033] Example 4

[0034] (1) In an ice-water bath, 70 mL of dichloromethane, 5 g of the intermediate (prepared in Example 1), 4.5 g of undecanoyl chloride, and 1.9 g of triethylamine were added to a flask, followed by stirring at room temperature for 15 h, distillation under reduced pressure, washing with water, and drying. The product was dissolved in dichloromethane, heated for volatilization, and cooled in an ice-water bath for recrystallization to obtain an alkane naphthalene styrene monomer.

[0035] (2) 100 mL of toluene and 1 g of acryloyl chloride grafted graphene (prepared in Example 1) were added to a flask, and after stirring and dispersing, 2.3 g of alkane naphthalene styrene monomer was added, and after stirring and dissolving, nitrogen was introduced, and 12.3 mg of azobisisobutyronitrile was added. The mixture was heated to 70° C. and stirred for reaction for 18 h. After filtering, the mixture was washed with dichloromethane and ethanol in turn, and dried to obtain alkane naphthalene polystyrene grafted graphene.

[0036] (3) Add 600 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 400 g of polypropylene, 50 g of alkane naphthalene polystyrene grafted graphene, and 0.3 g of antioxidant 1010 into a high-speed mixer, add the materials into a twin-screw extruder after blending, melt extrude, the screw temperature is 210° C., and the screw speed is 300 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0037] Comparative Example 1

[0038] (1) Add 900 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 100 g of polypropylene, and 0.3 g of antioxidant 1010 into a high-speed mixer, add the materials into a twin-screw extruder after blending, melt extrude, the screw temperature is 195° C., and the screw speed is 350 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0039] Comparative Example 2

[0040] (1) Add 900 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 100 g of polypropylene, 10 g of graphene oxide, and 0.3 g of antioxidant 1010 into a high-speed mixer, add the materials into a twin-screw extruder after blending, melt extrude, the screw temperature is 195° C., and the screw speed is 350 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0041] Comparative Example 3

[0042] (1) Add 900 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 100 g of polypropylene, 10 g of acryloyl chloride grafted graphene (prepared in Example 1), and 0.3 g of antioxidant 1010 to a high-speed mixer, and after blending, add the materials to a twin-screw extruder for melt extrusion at a screw temperature of 195° C. and a screw speed of 350 r / min; granulate to obtain a high-temperature resistant TPE thermoplastic elastomer material.

[0043] Comparative Example 4

[0044] (1) Add 100 mL of toluene and 1 g of acryloyl chloride grafted graphene into a flask, stir and disperse, then add 1.5 g of the intermediate (prepared in Example 1), stir and dissolve, then introduce nitrogen, add 8.7 mg of azobisisobutyronitrile, heat to 75° C. and stir to react for 12 h, filter, wash with dichloromethane and ethanol in turn, and dry to obtain naphthyl polystyrene grafted graphene.

[0045] (2) Add 900 g of hydrogenated styrene-butadiene-styrene block copolymer SEBS, 100 g of polypropylene, 10 g of naphthyl polystyrene grafted graphene, and 0.3 g of antioxidant 1010 into a high-speed mixer, add the materials into a twin-screw extruder after blending, melt extrude, the screw temperature is 195° C., and the screw speed is 350 r / min; granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

[0046] The UV-resistant TPE thermoplastic elastomer material was made into test specimens by an injection molding machine at an injection molding temperature of 200°C.

[0047] The tensile properties of the specimens were tested according to GB / T 528-2009.

[0048] The hardness of the sample was tested according to GB / T 531.1-2008 method.

[0049] The thermal properties of the samples were analyzed by thermogravimetric analysis. In a nitrogen atmosphere, the temperature was raised from 25°C to 700°C at a heating rate of 10°C / min. The performance test results are shown in Table 1.

[0050] Table 1: Performance Test

[0051]

[0052] After testing, the TPE thermoplastic elastomer material of Comparative Example 1 did not have graphene oxide added, and its tensile strength, elongation at break and hardness were lower. 5％ (temperature at 5% weight loss) and T 10％ (Temperature when weight loss is 10%) is low, and the mechanical properties and high temperature resistance are poor.

[0053] The TPE thermoplastic elastomer material of Comparative Example 2 is added with graphene oxide. Since graphene oxide is easy to agglomerate and has poor compatibility with hydrogenated styrene-butadiene-styrene block copolymer SEBS and polypropylene in the elastomer material, the reinforcing phase effect of graphene oxide is not good, and the tensile strength, elongation at break, hardness and T are low. 5％ and T 10％ The increase is smaller.

[0054] In comparative example 3, acryloyl chloride grafted graphene was added. After the surface of graphene oxide was organically modified, the dispersibility was improved to a certain extent, and the compatibility with hydrogenated styrene-butadiene-styrene block copolymer SEBS and polypropylene in the elastomer material was improved. The reinforcing phase effect of graphene oxide was better, and the tensile strength, elongation at break, and hardness were lower. 5％ and T 10％ The increase is relatively large.

[0055] Comparative Example 4: Using acryloyl chloride to graft graphene and intermediate Graft polymerization was carried out to introduce polystyrene molecular chains containing naphthalene ring structures on the graphene surface. The compatibility between the polystyrene molecular chains and the hydrogenated styrene-butadiene-styrene block copolymer SEBS was better, and the naphthalene ring structure had a higher thermal decomposition temperature and thermal stability, so that the naphthalene-polystyrene grafted graphene could further improve the tensile strength and other mechanical properties of the elastomer material, and T 5％ and T 10％ Higher, excellent high temperature resistance. However, the compatibility between the polystyrene molecular chain introduced on the graphene surface and polypropylene is poor.

[0056] Example 1-4 Graphene grafted with acryloyl chloride is subjected to graft polymerization reaction with alkane naphthalene styrene monomers, and polystyrene molecular chains containing alkyl long chains and naphthalene ring structures are introduced on the surface of graphene. The compatibility between the polystyrene molecular chains and SEBS is very good. At the same time, the introduced alkyl long chains have structural similarities with polypropylene, which can improve the compatibility between graphene and polypropylene, so that the graphene can be better dispersed in the elastomeric material composed of SEBS and polypropylene, further improving the tensile strength, elongation at break, hardness, T 5％ and T 10％ , showing excellent mechanical properties and high temperature resistance.

[0057] The above description is a preferred embodiment of the invention and is not intended to limit the invention. Any modifications, equivalent substitutions and improvements made within the spirit and principle of the invention should be included in the protection scope of the invention.

Claims

1. A method for preparing a high temperature resistant TPE thermoplastic elastomer material, characterized in that: The preparation method comprises the following steps: (1) Add toluene and acryloyl chloride grafted graphene into a flask, stir and disperse, then add the structural formula alkane naphthalene styrene monomer, n is any integer between 9 and 15; after stirring and dissolving, nitrogen is introduced, azobisisobutyronitrile is added, stirring and reacting, filtering, then washing with dichloromethane and ethanol in sequence, and drying to obtain alkane naphthalene polystyrene grafted graphene; (2) Add hydrogenated styrene-butadiene-styrene block copolymer SEBS, polypropylene, alkane naphthalene polystyrene grafted graphene, and antioxidant into a mixer, add the materials into a twin-screw extruder after blending, melt extrude, and granulate to obtain a high temperature resistant TPE thermoplastic elastomer material.

2. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 1, characterized in that: The reaction temperature in (1) is 70-85°C and the reaction time is 12-18h.

3. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 1, characterized in that: The mass ratio of acryloyl chloride grafted graphene, alkane naphthalene styrene monomer, and azobisisobutyronitrile in (1) is 100:(150-400):(0.87-2.34).

4. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 1, characterized in that: In the above (2), the mass ratio of hydrogenated styrene-butadiene-styrene block copolymer SEBS, polypropylene, and alkane naphthalene polystyrene grafted graphene is (60-90):(10-40):(1-5).

5. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 1, characterized in that: In the above (2), during melt extrusion, the screw temperature is 195-210° C. and the screw speed is 300-400 r / min.

6. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 3, characterized in that: The preparation method of the alkane naphthalene styrene monomer is: S1. Add ethanol, 4-chloromethylstyrene, 1-naphthylamine, sodium carbonate and water into a flask, heat to 50-65°C, stir and react for 6-10h, concentrate under reduced pressure, extract and recrystallize to obtain an intermediate; S2. In an ice-water bath, add dichloromethane, intermediate, alkyl acyl chloride compound, and triethylamine into a flask, and then stir and react at room temperature for 12-15 hours, and evaporate under reduced pressure, wash, and recrystallize to obtain an alkane naphthalene styrene monomer.

7. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 6, characterized in that: In the S1, the mass ratio of 4-chloromethylstyrene, 1-naphthylamine and sodium carbonate is 100:(93-122):(0.72-0.86).

8. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 6, characterized in that: In S2, the mass ratio of the intermediate, the alkyl acyl chloride compound, and triethylamine is 100:(74-106):(38-46).

9. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 8, characterized in that: The structural formula of the alkyl acyl chloride compound is n is any integer between 9 and 15.

10. The method for preparing a high temperature resistant TPE thermoplastic elastomer material according to claim 3, characterized in that: The preparation method of the acryloyl chloride grafted graphene comprises the following steps: adding N,N-dimethylformamide, graphene oxide and triethylamine into a flask, introducing nitrogen after ultrasonic dispersion, adding acryloyl chloride in an ice bath, stirring for reaction, filtering, washing and drying to obtain the acryloyl chloride grafted graphene.

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