CN114736481B - Gasoline-resistant TPE material - Google Patents
Gasoline-resistant TPE material Download PDFInfo
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- CN114736481B CN114736481B CN202210137184.0A CN202210137184A CN114736481B CN 114736481 B CN114736481 B CN 114736481B CN 202210137184 A CN202210137184 A CN 202210137184A CN 114736481 B CN114736481 B CN 114736481B
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Abstract
The invention relates to the technical field of thermoplastic elastomers, and discloses a gasoline-resistant TPE material which comprises the following raw materials in parts by weight: 30-40 parts of SEBS rubber, 10-20 parts of ethylene propylene diene monomer rubber, 10-20 parts of polyethylene octene co-elastomer, 5-10 parts of polypropylene, 2-5 parts of monomer resin, 20-30 parts of white oil and 9-18 parts of oil-resistant auxiliary agent. The TPE plastic prepared by taking the SEBS thermoplastic elastomer as a matrix and matching with other components has good elasticity, strength and flexibility and excellent comprehensive performance; the added oil-resistant additive has better compatibility with SEBS matrix and polyolefin materials while improving the gasoline resistance, and improves the integral combination and stability.
Description
Technical Field
The invention relates to the technical field of thermoplastic elastomers, in particular to a gasoline-resistant TPE material.
Background
With the rapid development of economy, the enhancement of environmental protection consciousness of human beings and the continuous improvement of product requirements are carried out, and the demand of people for high-demand plastics is increasing. The TPE (Thermoplastic Elastomer thermoplastic elastomer) is a characteristic material with high elasticity, high strength and high rebound resilience of rubber, and has the characteristics of injection molding, is nontoxic and environment-friendly, has excellent colorability, weather resistance and temperature resistance, has excellent processing performance, can be recycled, can be coated and bonded with matrix materials such as PP, PC, PS, ABS and the like, and can also be independently molded, and the TPE has the processing performance of thermoplastic plastics and the physical properties of vulcanized rubber, namely the advantageous combination of the advantages of plastics and rubber, so that the TPE is actively occupied the field of the vulcanized rubber. However, the price of the TPE is still higher, the yield is lower, the gasoline resistance is poor, and improvement is urgently needed.
However, most of the existing oil-resistant rubbers are nitrile rubber, chloroprene rubber and fluororubber, and the defects of the existing oil-resistant rubbers are poor mechanical property, large compression set, low rebound rate, rough hand feeling of products, poor high-low temperature impact property and the like; some of them use SEBS as a base material, and add nitrile rubber, chloroprene rubber and fluororubber to improve oil resistance, for example, chinese patent publication No. CN106832832a discloses an oil-resistant, cold-resistant and wear-resistant sole material and a preparation method thereof, and the oil-resistant, cold-resistant and wear-resistant sole material is composed of the following raw materials: styrene (S) -ethylene (E)/butylene (B) -styrene (S) forms a block copolymer (SEBS), thermoplastic polyurethane elastomer rubber (TPU), nitrile rubber, inorganic filler, heat stabilizer and hindered amine light stabilizer. The method has the defects that the compatibility of the nitrile rubber and the SEBS is extremely poor, the compatibilizer is needed to be added to improve the compatibility, the soft and fine hand feeling element of the SEBS can be greatly influenced, and the mechanical property and rebound resilience of the product are greatly deteriorated.
Disclosure of Invention
In order to solve the technical problems, the invention provides the gasoline-resistant TPE material, which takes the SEBS thermoplastic elastomer as a matrix and is matched with other component materials, so that the gasoline resistance is improved, and meanwhile, the TPE plastic is ensured to have good mechanical property and elasticity.
The specific technical scheme of the invention is as follows:
the invention provides a gasoline-resistant TPE material, which comprises the following raw materials in parts by weight: 30-40 parts of SEBS rubber, 10-20 parts of ethylene propylene diene monomer rubber, 10-20 parts of polyethylene octene co-elastomer, 5-10 parts of polypropylene, 2-5 parts of monomer resin and 20-30 parts of polyethylene octene co-elastomer
White oil and 9-18 parts of oil-resistant auxiliary agent.
The SEBS is a linear triblock copolymer taking polystyrene as a terminal section and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as a middle elastic block, and the SEBS does not contain unsaturated double bonds, so that the SEBS has excellent ageing resistance, has plasticity and high elasticity, and can be processed and used without vulcanization. The modified polypropylene composite material also has good solubility, blending performance and excellent oil-filling performance, can be blended with other polyolefin materials, and optimizes the surface texture and weather resistance and ageing resistance by blending with polypropylene (PP) and white oil. The main characteristic of Ethylene Propylene Diene Monomer (EPDM) is its excellent oxidation resistance, ozone resistance and erosion resistance, and can absorb a large amount of filler and oil with little influence on the characteristics, so that the rubber compound with low cost can be manufactured. The Polyethylene Octene Elastomer (POE) has good rebound resilience and flexibility, low hardness and excellent cold resistance, can be used for toughening PP, improves the impact strength of the PP at normal temperature and low temperature, and has good fluidity to improve the dispersion effect of the oil-resistant auxiliary agent. The oil-resistant additive is used for improving the gasoline resistance of the TPE plastic, improving the overall polarity, preventing the TPE plastic from being permeated and swelled in nonpolar oil, and reducing the strength and other mechanical properties of the TPE plastic. Finally, the TPE plastic formula which is low in price, high in yield, excellent in performance, meets the gasoline resistance requirement of customers and is environment-friendly is obtained.
Preferably, the weight parts of the SEBS rubber are larger than the total weight parts of the ethylene propylene diene monomer rubber and the polyethylene octene co-elastomer, and the ethylene propylene diene monomer rubber and the polyethylene octene co-elastomer are the same.
The styrene block is contained in the SEBS rubber, and compared with the ethylene propylene diene monomer rubber and polyethylene octene co-elastomer, the SEBS rubber has better oil resistance.
Preferably, the content of ethylene structural units in the polyethylene octene co-elastomer is 30-50%, and the content of octene structural units is 50-70%; the weight average molecular weight of the polyethylene octene co-elastomer is 100-300 kg/mol.
Preferably, the monomer resin is an aromatic monomer resin or an aliphatic monomer resin having a molecular weight of 2000 to 10000.
In a TPE plastic system, monomer resin is used for improving processability and mechanical property and viscoelasticity, the monomer resin migrates into a styrene phase in the SEBS and is combined with styrene to form physical crosslinking, and the styrene phase is reinforced, so that the content of styrene in the SEBS is increased, the hardness is further increased, and the control of the molecular weight of the monomer resin can ensure that the TPE plastic has better hardness and elasticity.
Preferably, the glass transition temperature of the aromatic monomer resin or the aliphatic monomer resin is 90 to 150 ℃.
Preferably, the gasoline-resistant TPE material also comprises 1 to 3 parts of filler and 0.1 to 0.8 part of antioxidant.
Preferably, the filler is carbon black, white carbon black, silica, calcium carbonate or montmorillonite; the antioxidant is one or more of phenolic antioxidants and phosphite antioxidants.
Preferably, the preparation method of the oil-resistant auxiliary agent comprises the following steps:
(1) Ti is mixed with 3 C 2 T x Preparation of Ti in tetrahydrofuran solution 3 C 2 T x Adding acrylamide into the dispersion liquid, stirring, adding a mixed solution containing styrene, acrylonitrile, tertiary dodecyl mercaptan and ethanol, and carrying out polymerization reaction; the Ti is 3 C 2 T x The mass ratio of the acrylamide, the styrene and the acrylonitrile is 0.1-1: 10-20: 25-40: 25-40;
(2) Adding the product obtained in the step (1) into acetic acid aqueous solution of chitosan, stirring, then adding di-tert-butyl peroxide and maleic anhydride for reaction, and then slowly adding PVDF resin under the condition of heating and stirring, wherein the mass ratio of the product obtained in the step (1), chitosan, maleic anhydride and PVDF resin is 20-40: 5 to 9:1 to 3: and 2-5, finally obtaining the oil-resistant auxiliary agent.
The oil-resistant additive can improve the gasoline resistance of TPE plastics, and the acrylamide is copolymerized with styrene-acrylonitrile to obtain SAN-like resin which is a polar polymer, has good chemical medium resistance, high impact resistance and high mechanical property, and the compatibility with polyolefin materials can be improved to a certain extent by adding the acrylamide for copolymerization. The polarity difference between the PVDF resin and the nonpolar oil is larger because of containing polar group fluorine atoms, and the PVDF resin can be added to improve the oil resistance, but the compatibility between the polar copolymer and the SEBS matrix is poor. The chitosan contains hydroxyl and amino polar groups, so that the oil resistance can be improved, but also contains a high molecular long carbon chain, so that the compatibility between the chitosan and SEBS and polyolefin materials can be improved, and the chitosan is grafted with acrylamide in SAN-like resin through maleic anhydride to form a crosslinked macromolecular chain, so that the combination property and stability are improved. In addition, added Ti 3 C 2 T x Also present in a large amount are hydroxyl groups, amino groups, fluoro groups, etc., in addition to being able to increaseBesides oil resistance, the functional group of the modified polyethylene glycol sulfonate and other components of the oil-resistant auxiliary agent have good compatibility, especially form a cross-linked network structure with the PVDF resin by means of hydrogen bond and Van der Waals force combination together with the hydroxyl on chitosan, so that the synergistic stability among the components of the oil-resistant auxiliary agent is optimized. Ti (Ti) 3 C 2 T x The TPE plastic has larger specific surface area and stronger mechanical property, can be used as reinforcing filler of TPE plastic, and improves the comprehensive performance of the TPE plastic.
Preferably, in step (1), the Ti is 3 C 2 T x Ti in the dispersion 3 C 2 T x Wherein T is present at a concentration of 2 to 6mg/mL x Is a surface end group comprising hydroxyl, fluorine, oxygen, or a combination thereof; the polymerization reaction is as follows: the reaction is carried out for 1 to 2 hours at the temperature of 150 to 170 ℃ and then for 0.5 to 1 hour at the temperature of 180 to 220 ℃.
Ti 3 C 2 T x Because of the high surface energy, agglomeration is easy to generate, the dispersion of the TPE plastic is improved by dispersing the TPE plastic in tetrahydrofuran, but the concentration in the dispersion liquid still affects the combination property with other components, and finally the mechanical property of the TPE plastic is formed.
Preferably, in the step (2), the concentration of chitosan in the acetic acid aqueous solution of chitosan is 1-4 mg/mL, and the volume fraction of acetic acid is 3-10%; the molecular weight of the chitosan is 2 x 10 4 ～10*10 4 The method comprises the steps of carrying out a first treatment on the surface of the The reaction is carried out for 5-8 h at 30-60 ℃; the PVDF resin has a molecular weight of 30 x 10 4 ～60*10 4 The method comprises the steps of carrying out a first treatment on the surface of the The heating and stirring are carried out for 2-4 hours at 50-70 ℃.
The concentration of chitosan affects its dispersibility, while the molecular weight of chitosan determines its viscosity, and affects the degree of reaction with and binding to the product obtained in step (1). The higher the molecular weight of the PVDF resin, the higher the viscosity, the more likely the aggregation and swelling are formed at the time of addition, the dispersibility in the mixture becomes poor, and the fluorine content of the single molecular chain is also reduced at the time of lower molecular weight, and the oil resistance is poor.
Compared with the prior art, the invention has the following advantages:
(1) The TPE plastic obtained by taking the SEBS thermoplastic elastomer as a matrix and matching with other components has good elasticity, strength and flexibility and excellent comprehensive performance;
(2) The added oil-resistant additive has better compatibility with SEBS matrix and polyolefin materials while improving the gasoline resistance, and improves the integral combination and stability.
Detailed Description
The invention is further described below with reference to examples.
General examples
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 30-40 parts of SEBS rubber, 10-20 parts of ethylene propylene diene monomer rubber, 10-20 parts of polyethylene octene co-elastomer, 5-10 parts of polypropylene, 2-5 parts of monomer resin, 20-30 parts of white oil and 9-18 parts of oil-resistant auxiliary agent.
The weight parts of the SEBS rubber are larger than the total weight parts of the ethylene propylene diene monomer rubber and the polyethylene octene co-elastomer, and the ethylene propylene diene monomer rubber and the polyethylene octene co-elastomer are the same; the content of ethylene structural units in the polyethylene octene co-elastomer is 30-50%, the content of octene structural units is 50-70%, and the weight average molecular weight is 100-300 kg/mol; the monomer resin is aromatic monomer resin or aliphatic monomer resin with molecular weight of 2000-10000 and glass transition temperature of 90-150 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) Ti is mixed with 3 C 2 T x Preparing Ti with concentration of 2-6 mg/mL in tetrahydrofuran solution 3 C 2 T x Adding acrylamide into the dispersion liquid, stirring, adding a mixed solution containing styrene, acrylonitrile, tertiary dodecyl mercaptan and ethanol, performing polymerization reaction, reacting for 1-2 hours at 150-170 ℃ and then reacting for 0.5-1 hour at 180-220 ℃; the Ti is 3 C 2 T x The mass ratio of the acrylamide, the styrene and the acrylonitrile is 0.1-1: 10-20: 25-40: 25-40;
(2) Adding the product obtained in step (1) to a composition comprising chitosan having a molecular weight of 2 x 10 4 ～10*10 4 Chitosan in acetic acid aqueous solutionThe concentration of chitosan in the acetic acid aqueous solution is 1-4 mg/mL, and the volume fraction of acetic acid is 3-10%; stirring, adding di-tert-butyl peroxide and maleic anhydride, reacting at 30-60 deg.C for 5-8 hr, and slowly adding 30-10 molecular weight under stirring at 50-70 deg.C 4 ～60*10 4 Stirring for 2-4 h, wherein the mass ratio of the obtained substance in the step (1), chitosan, maleic anhydride and PVDF resin is 20-40: 5 to 9:1 to 3: and 2-5, finally obtaining the oil-resistant auxiliary agent.
In addition, the gasoline-resistant TPE material can also comprise 1 to 3 parts of filler and 0.1 to 0.8 part of antioxidant. Wherein the filler is carbon black, white carbon black, silicon dioxide, calcium carbonate or montmorillonite, and the antioxidant is one or more of phenolic antioxidants and phosphite antioxidants.
Example 1
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber and 15 parts of
The polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 3mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 6 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride are added to react for 6 hours at 55 ℃, and then 0.8g of the mixture with the molecular weight of 40 x 10 is slowly added under the stirring condition with the temperature of 60 DEG C 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Example 2
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 30 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber and 15 parts of
The polyethylene octene co-elastomer, 8 parts of polypropylene, 4 parts of monomer resin, 20 parts of white oil and 12 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 30%, the content of octene structural units is 70%, and the weight average molecular weight is 250kg/mol; the monomer resin is aromatic monomer resin with molecular weight of 5000 and glass transition temperature of 110 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 4mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 2.5g of styrene, 2.5g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 150 ℃ before reacting for 0.5 hour at 210 ℃;
(2) Adding 6g of the product obtained in the step (1) into 2mg/mL of acetic acid aqueous solution of chitosan, wherein the acetic acid aqueous solution of the chitosan is prepared by 1.68g of chitosan with molecular weight of 8 x 10 4 Is prepared from chitosan and acetic acid with the volume fraction of 5 percent; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.48g of maleic anhydride are added for reaction for 7 hours at 50 ℃, and then 0.8g of the catalyst with molecular weight of 30 x 10 is slowly added under the stirring condition with the temperature of 65 DEG C 4 And stirring for 3 hours to finally obtain the oil-resistant auxiliary agent.
Example 3
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber and 15 parts of
The polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 4mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 2.5g of styrene, 2.5g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 150 ℃ before reacting for 0.5 hour at 210 ℃;
(2) Adding 6g of the product obtained in the step (1) into 2mg/mL of acetic acid aqueous solution of chitosan, wherein the acetic acid aqueous solution of the chitosan is prepared by 1.68g of chitosan with molecular weight of 8 x 10 4 Is prepared from chitosan and acetic acid with the volume fraction of 5 percent; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.48g of maleic anhydride are added for reaction for 7 hours at 50 ℃, and then 0.8g of the catalyst with molecular weight of 30 x 10 is slowly added under the stirring condition with the temperature of 65 DEG C 4 And stirring for 3 hours to finally obtain the oil-resistant auxiliary agent.
Example 4
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber, 15 parts of polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil, 15 parts of oil-resistant auxiliary agent, 1-3 parts of calcium carbonate and 0.1-0.8 part of tri (2, 4-di-tert-butylphenyl) phosphite ester.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 3mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 6 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride are added to react for 6 hours at 55 ℃, and then 0.8g of the mixture with the molecular weight of 40 x 10 is slowly added under the stirring condition with the temperature of 60 DEG C 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Comparative example 1
The difference from example 1 is that: in the preparation method of the oil-resistant additive, ti 3 C 2 T x Ti in the dispersion 3 C 2 T x The concentration of (C) was 0.5mg/mL.
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber, 15 parts of polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to obtainTo a concentration of 0.5mg/mL Ti 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 3mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 6 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride are added to react for 6 hours at 55 ℃, and then 0.8g of the mixture with the molecular weight of 40 x 10 is slowly added under the stirring condition with the temperature of 60 DEG C 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Comparative example 2
The difference from example 1 is that: in the preparation method of the oil-resistant additive, the concentration of chitosan in the acetic acid aqueous solution of chitosan is 6mg/mL.
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber, 15 parts of polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 6mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 6 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride are added to react for 6 hours at 55 ℃, and then 0.8g of the mixture with the molecular weight of 40 x 10 is slowly added under the stirring condition with the temperature of 60 DEG C 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Comparative example 3
The difference from example 1 is that: in the preparation method of the oil-resistant additive, the molecular weight of chitosan is 18 x 10 4 。
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber, 15 parts of polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 3mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 18 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; the mixed solution is stirred and then added with 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride to react for 6 hours at 55 ℃, and then the temperature is 60 DEG CSlowly adding 0.8g of a polymer having a molecular weight of 40 x 10 under stirring at a temperature of 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Comparative example 4
The difference from example 1 is that: in the preparation method of the oil-resistant additive, the molecular weight of the PVDF resin is 80 x 10 4 。
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber, 15 parts of polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 3mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 6 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride are added to react for 6 hours at 55 ℃, and then 0.8g of the mixture with the molecular weight of 80 x 10 is slowly added under the stirring condition with the temperature of 60 DEG C 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Comparative example 5
The difference from example 1 is that: in the preparation method of the oil-resistant additive, the molecular weight of the PVDF resin is 20 x 10 4 。
The gasoline-resistant TPE material comprises the following raw materials in parts by weight: 40 parts of SEBS rubber, 15 parts of ethylene propylene diene monomer rubber, 15 parts of polyethylene octene co-elastomer, 6 parts of polypropylene, 3 parts of monomer resin, 22 parts of white oil and 15 parts of oil-resistant auxiliary agent.
Wherein the content of ethylene structural units in the polyethylene octene co-elastomer is 40%, the content of octene structural units is 60%, and the weight average molecular weight is 200kg/mol; the monomer resin is an aromatic monomer resin with a molecular weight of 7000 and a glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti 3 C 2 T x Adding into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL 3 C 2 T x Adding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan and 20mL of ethanol, performing polymerization reaction, reacting for 1.5 hours at 160 ℃ before reacting for 0.5 hour at 200 ℃;
(2) Adding 6g of the product obtained in the step (1) into an aqueous solution of chitosan acetic acid with the concentration of 3mg/mL, wherein the aqueous solution of chitosan acetic acid is prepared from 1.2g of chitosan with the molecular weight of 6 x 10 4 Is prepared from chitosan with the volume fraction of 7 percent of acetic acid; after the mixed solution is stirred, 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride are added to react for 6 hours at 55 ℃, and then 0.8g of the mixture with the molecular weight of 40 x 10 is slowly added under the stirring condition with the temperature of 60 DEG C 4 And stirring for 4 hours to finally obtain the oil-resistant auxiliary agent.
Performance testing
Tensile strength and elongation at break: testing according to standard GB/T2951;
tensile strength change rate and elongation at break change rate: after immersion in petrol for 20h at a temperature of 23℃the test was carried out according to standard GB/T2951.
Table 1 results of performance testing of gasoline resistant TPE materials
According to the performance test results in table 1, the gasoline-resistant TPE materials obtained in examples 1 to 4 completely have gasoline resistance requirements, and are excellent in elasticity, mechanical properties and stability. Combining example 1 and comparative example 1, ti 3 C 2 T x Too high a concentration in the dispersion may tend to cause agglomeration due to its higher surface energy, affect the bonding with other components, and reduce the mechanical properties of the TPE material. In combination with examples 1 and comparative examples 2 to 3, when the chitosan concentration is too high or the molecular weight is too large, the viscosity is too high, the dispersibility is poor, the chitosan molecular chain is easily converted into a coil structure which is mutually wound from a stretching chain structure, the reaction is not facilitated to carry out graft crosslinking, and after the stability of the oil-resistant auxiliary agent is reduced, the mechanical property and the oil resistance are also reduced. When the chitosan concentration is too low, the content of hydroxyl groups and amino groups decreases, so that the oil resistance decreases, the compatibility with the matrix becomes poor, and the synergistic stability with the PVDF resin becomes poor. In combination with examples 1 and comparative examples 4 to 5, the higher the molecular weight of the PVDF resin, the greater the viscosity, the more likely to form an agglomeration swelling upon addition, the poorer the dispersibility in the mixture, and the lower the mechanical properties; on the other hand, when the molecular weight of the PVDF resin is low, the fluorine content of a single molecular chain is also reduced, and the oil resistance is poor.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The gasoline-resistant TPE material is characterized by comprising the following raw materials in parts by weight: 30-40 parts of SEBS rubber, 10-20 parts of ethylene propylene diene monomer rubber, 10-20 parts of polyethylene octene co-elastomer, 5-10 parts of polypropylene, 2-5 parts of monomer resin, 20-30 parts of white oil and 9-18 parts of oil-resistant auxiliary agent;
the preparation method of the oil-resistant auxiliary agent comprises the following steps:
(1) Ti is mixed with 3 C 2 T x Preparation of Ti in tetrahydrofuran solution 3 C 2 T x Adding acrylamide into the dispersion liquid, stirring, adding a mixed solution containing styrene, acrylonitrile, tertiary dodecyl mercaptan and ethanol, and carrying out polymerization reaction; the Ti is 3 C 2 T x The mass ratio of the acrylamide to the styrene to the acrylonitrile is 0.1-1: 10-20: 25-40: 25-40 parts;
(2) Adding the product obtained in the step (1) into acetic acid aqueous solution of chitosan, stirring, then adding di-tert-butyl peroxide and maleic anhydride for reaction, and then slowly adding PVDF resin under the condition of heating and stirring, wherein the mass ratio of the product obtained in the step (1), chitosan, maleic anhydride and PVDF resin is 20-40: 5-9: 1-3: and 2-5, finally obtaining the oil-resistant auxiliary agent.
2. The gasoline resistant TPE material of claim 1 wherein the SEBS rubber is greater than the total weight parts of the ethylene propylene diene monomer and polyethylene octene co-elastomer and the ethylene propylene diene monomer and polyethylene octene co-elastomer are the same.
3. The gasoline-resistant TPE material according to claim 1, wherein the polyethylene octene co-elastomer has an ethylene structural unit content of 30-50% and an octene structural unit content of 50-70%; the weight average molecular weight of the polyethylene octene co-elastomer is 100-300 kg/mol.
4. The gasoline resistant TPE material according to claim 1, wherein the monomer resin is an aromatic monomer resin or an aliphatic monomer resin having a molecular weight of 2000 to 10000.
5. The gasoline resistant TPE material of claim 4 wherein the aromatic monomer resin or aliphatic monomer resin has a glass transition temperature of 90 to 150 ℃.
6. The gasoline resistant TPE material of claim 1 further comprising 1-3 parts filler and 0.1-0.8 parts antioxidant.
7. The gasoline resistant TPE material of claim 6 wherein the filler is carbon black, white carbon black, silica, calcium carbonate or montmorillonite; the antioxidant is one or more of phenolic antioxidants and phosphite antioxidants.
8. The gasoline resistant TPE material of claim 1 wherein in step (1) the Ti 3 C 2 T x Ti in the dispersion 3 C 2 T x The concentration of (2) to (6) mg/mL; the polymerization reaction is as follows: the reaction is carried out for 1 to 2 hours at the temperature of 150 to 170 ℃ and then for 0.5 to 1 hour at the temperature of 180 to 220 ℃.
9. The gasoline-resistant TPE material according to claim 1, wherein in the step (2), the concentration of chitosan in the aqueous solution of acetic acid of chitosan is 1-4 mg/mL, and the volume fraction of acetic acid is 3-10%; the molecular weight of the chitosan is 2 x 10 4 ~10*10 4 The method comprises the steps of carrying out a first treatment on the surface of the The reaction is carried out for 5-8 hours at the temperature of 30-60 ℃; the PVDF resin has a molecular weight of 30 x 10 4 ~60*10 4 The method comprises the steps of carrying out a first treatment on the surface of the And stirring for 2-4 hours at the temperature of 50-70 ℃ by heating and stirring.
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