CN114736481A - Gasoline-resistant TPE material - Google Patents
Gasoline-resistant TPE material Download PDFInfo
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- CN114736481A CN114736481A CN202210137184.0A CN202210137184A CN114736481A CN 114736481 A CN114736481 A CN 114736481A CN 202210137184 A CN202210137184 A CN 202210137184A CN 114736481 A CN114736481 A CN 114736481A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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 obtained by taking the SEBS thermoplastic elastomer as the matrix and matching with other components has good elasticity, strength and flexibility and excellent comprehensive performance; the added oil-resistant auxiliary agent has better compatibility with SEBS matrix and polyolefin material while improving the gasoline resistance, and improves the integral associativity 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 awareness and the continuous improvement of product requirements of human beings, people have more and more requirements on high-requirement plastics. TPE (Thermoplastic Elastomer) is a material with the characteristics of high elasticity, high strength and high resilience of rubber, can be processed by injection molding, has the advantages of no toxicity, environmental protection, excellent colorability, weather resistance and temperature resistance, excellent processability, can be recycled, can be coated and adhered with matrix materials such as PP, PC, PS, ABS and the like, and can be formed independently. However, the price of TPE is still high, the yield is low, 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 conventional oil-resistant rubbers are that the mechanical property is poor, the compression permanent deformation is large, the rebound rate is low, the product hand feeling is rough, the high-temperature and low-temperature impact properties are poor, and the like; for example, chinese patent publication No. CN106832832A discloses an oil-resistant, cold-resistant, and wear-resistant sole material and a preparation method thereof, wherein 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) to form 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, a compatibilizer is required to be added to improve the compatibility, the soft and fine element of the SEBS can be greatly influenced, and the mechanical property and the rebound resilience of the product are greatly deteriorated.
Disclosure of Invention
In order to solve the technical problems, the invention provides a gasoline-resistant TPE material, which takes an SEBS thermoplastic elastomer as a matrix and is matched with other component materials, so that the gasoline resistance is improved, and the TPE plastic has 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, 10-20 parts of polyethylene octene co-elastomer, 5-10 parts of polypropylene, 2-5 parts of monomer resin and 20-30 parts of ethylene propylene diene monomer
White oil and 9-18 parts of oil-resistant auxiliary agent.
SEBS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-butylene copolymer obtained by hydrogenating polybutadiene as a middle elastic block, does not contain unsaturated double bonds, has excellent aging resistance, has plasticity and high elasticity, and can be processed and used without vulcanization. The modified polypropylene has good solubility, blending performance and excellent oil-filling performance, can be blended with other polyolefin materials, and optimizes surface texture, 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 corrosion resistance, and can absorb a large amount of filler and oil without much influence on the characteristic, so that the EPDM can be made into a rubber compound with low cost. The polyethylene octene co-elastomer (POE) has good rebound resilience and flexibility, very low hardness and excellent cold resistance, can be used for toughening PP, improving the impact strength of PP at normal temperature and low temperature, and has good fluidity to improve the dispersion effect of the oil-resistant additive. The oil-resistant auxiliary agent is used for improving the gasoline resistance of the TPE plastic, improving the overall polarity, preventing the TPE plastic from permeating and swelling in nonpolar oil, and reducing the strength and other mechanical properties of the TPE plastic. Finally, the TPE plastic formula which has low price, high yield and excellent performance, meets the requirement of gasoline resistance of customers and is environment-friendly is obtained.
Preferably, the weight part of the SEBS rubber is more than the total weight part of the ethylene-propylene-diene rubber and the polyethylene octene co-elastomer, and the weight parts of the ethylene-propylene-diene rubber and the polyethylene octene co-elastomer are the same.
The SEBS rubber contains a styrene block, and has better oil resistance compared with ethylene propylene diene monomer and polyethylene octene co-elastomer.
Preferably, the content of the ethylene structural unit in the polyethylene octene co-elastomer is 30-50%, and the content of the octene structural unit in the polyethylene octene co-elastomer is 50-70%; the weight average molecular weight of the polyethylene octene co-elastomer is 100-300 kg/mol.
Preferably, the monomer resin is aromatic monomer resin or aliphatic monomer resin with the molecular weight of 2000-10000.
In a TPE plastic system, monomer resin is used for improving processability and improving mechanical property and viscoelasticity, the monomer resin migrates to a styrene phase in SEBS, and is combined with styrene to form physical crosslinking, and the styrene phase is enhanced, so that the content of the styrene in the SEBS is improved, the hardness is improved, and the molecular weight of the monomer resin is controlled to ensure that the TPE plastic has better hardness and elasticity.
Preferably, the aromatic monomer resin or the aliphatic monomer resin has a glass transition temperature of 90 to 150 ℃.
Preferably, the gasoline-resistant TPE material further comprises 1-3 parts of filler and 0.1-0.8 part of antioxidant.
Preferably, the filler is carbon black, white carbon black, silica, calcium carbonate or montmorillonite; the antioxidant is one or more of phenol antioxidant and phosphite antioxidant.
Preferably, the preparation method of the oil-resistant auxiliary agent comprises the following steps:
(1) mixing Ti3C2TxPreparing Ti in tetrahydrofuran solution3C2TxAdding acrylamide into the dispersion liquid, stirring, adding a mixed solution containing styrene, acrylonitrile, tert-dodecyl mercaptan and ethanol, and carrying out polymerization reaction; the Ti3C2TxThe mass ratio of acrylamide to styrene to acrylonitrile is 0.1-1: 10-20: 25-40: 25-40;
(2) adding the substance obtained in the step (1) into an acetic acid aqueous solution of chitosan, stirring, 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 substance obtained in the step (1) to the chitosan to the maleic anhydride to the PVDF resin is 20-40: 5-9: 1-3: and 2-5, finally obtaining the oil-resistant assistant.
The oil-resistant auxiliary agent can improve the gasoline resistance of TPE plastic, and acrylamide participates in the copolymerization of styrene-acrylonitrile to obtain SAN-like resin which is a polar polymer and has good chemical medium resistance and higher impact resistance and mechanical property, and the compatibility with polyolefin materials can be improved to a certain extent by adding the acrylamide for copolymerization. The PVDF resin has larger polarity difference with non-polar oils due to the fluorine atoms containing polar groups, the oil resistance can be improved by adding the PVDF resin, 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 with SEBS and polyolefin materials can be improved, and the chitosan is grafted with acrylamide in SAN-like resin through maleic anhydride to form a cross-linked macromolecular chain, so that the binding property and the stability are improved. In addition, added Ti3C2TxAnd a large amount of hydroxyl, amino, fluorine and the like exist, so that the oil resistance can be improved, the compatibility between the functional group and other components of the oil-resistant auxiliary agent is good, and particularly, the functional group and the hydroxyl on the chitosan form a cross-linked network structure combined with the PVDF resin by virtue of hydrogen bonds and van der Waals forces, so that the synergistic stability among the components of the oil-resistant auxiliary agent is optimized. Ti3C2TxThe TPE plastic has larger specific surface area and stronger mechanical property, can be used as a reinforcing filler of TPE plastic, and improves the comprehensive performance of the TPE plastic.
Preferably, in the step (1), the Ti3C2TxTi in the dispersion3C2TxThe concentration of (a) is 2-6 mg/mL, wherein TxIs a surface terminal group comprising hydroxyl, fluorine, oxygen, or a combination thereof; the polymerization reaction is as follows: the reaction is carried out for 1-2 h at a temperature of 150-170 ℃ and then for 0.5-1 h at a temperature of 180-220 ℃.
Ti3C2TxBecause of its high surface energy, it is easy to agglomerate, so that its dispersibility can be raised by dispersing it in tetrahydrofuran, but its concentration in the dispersion can still affect the binding property with other components and finally formAnd (3) mechanical property of TPE plastic.
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 chitosan has a molecular weight of 2 x 104～10*104(ii) a The reaction is carried out for 5-8 h at 30-60 ℃; the molecular weight of the PVDF resin is 30 x 104～60*104(ii) a The heating and stirring are carried out for 2-4 h at 50-70 ℃.
The concentration of chitosan affects the dispersibility, while the molecular weight of chitosan determines the viscosity, and affects the degree of reaction and binding with the product obtained in step (1). The higher the molecular weight of the PVDF resin, the higher the viscosity, the more likely it is to form an agglomerated swelling during the addition, the less the dispersibility in the mixture, and the lower the molecular weight, the lower the fluorine content of the single molecular chain, and the less the oil resistance.
Compared with the prior art, the invention has the following advantages:
(1) the TPE plastic obtained by taking the SEBS thermoplastic elastomer as the matrix and matching with other components has good elasticity, strength and flexibility and excellent comprehensive performance;
(2) the added oil-resistant auxiliary agent has better compatibility with SEBS matrix and polyolefin material while improving the gasoline resistance, and improves the integral associativity and stability.
Detailed Description
The present invention will be further described with reference to the following 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.
Wherein the weight part of the SEBS rubber is more than the total weight part of the ethylene propylene diene monomer and the polyethylene octene co-elastomer, and the weight parts of the ethylene propylene diene monomer 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 the molecular weight of 2000-10000 and the glass transition temperature of 90-150 ℃.
The preparation method of the oil-resistant auxiliary agent comprises the following steps:
(1) mixing Ti3C2TxPreparing Ti with the concentration of 2-6 mg/mL in tetrahydrofuran solution3C2TxAdding acrylamide into the dispersion liquid, stirring, adding a mixed solution containing styrene, acrylonitrile, tert-dodecyl mercaptan and ethanol, carrying out polymerization reaction, reacting for 1-2 hours at the temperature of 150-170 ℃, and reacting for 0.5-1 hour at the temperature of 180-220 ℃; the Ti3C2TxAnd the mass ratio of acrylamide to styrene to acrylonitrile is 0.1-1: 10-20: 25-40: 25-40;
(2) adding the product obtained in the step (1) into chitosan with molecular weight of 2 x 104～10*104In the acetic acid aqueous solution of (3), 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%; stirring, adding di-tert-butyl peroxide and maleic anhydride, reacting for 5-8 h at 30-60 ℃, and slowly adding the mixture with the molecular weight of 30 x 10 under the stirring condition of the temperature of 50-70 DEG C4～60*104Stirring the PVDF resin for 2-4 h, wherein the mass ratio of the substance obtained in the step (1) to the chitosan to the maleic anhydride to the PVDF resin is 20-40: 5-9: 1-3: and 2-5, finally obtaining the oil-resistant auxiliary agent.
In addition, the gasoline-resistant TPE material can also comprise 1-3 parts of filler and 0.1-0.8 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 phenol antioxidant and phosphite antioxidant.
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 ethylene propylene diene monomer rubber
The oil-resistant polypropylene composite material comprises a 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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 160 ℃ for 1.5 hours, and then reacting at 200 ℃ for 0.5 hour;
(2) adding 6g of the product obtained in the step (1) into 3mg/mL aqueous acetic acid solution of chitosan, wherein the molecular weight of the aqueous acetic acid solution of chitosan is 6 x 10 from 1.2g4The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 deg.C for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 40 x 10 at 60 deg.C under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
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 ethylene propylene diene monomer rubber
The composite material comprises a 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 250 kg/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 Ti3C2TxAdding tetrahydrofuran solutionTo obtain Ti with the concentration of 4mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 2.5g of styrene, 2.5g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 150 ℃ for 1.5h, and then reacting at 210 ℃ for 0.5 h;
(2) adding 6g of the product obtained in the step (1) into 2mg/mL aqueous solution of chitosan in acetic acid, wherein the aqueous solution of chitosan in acetic acid is composed of 1.68g of chitosan with the molecular weight of 8 x 104The chitosan and acetic acid with the volume fraction of 5 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.48g of maleic anhydride, reacting at 50 deg.C for 7h, and slowly adding 0.8g of a polymer with a molecular weight of 30 x 10 at 65 deg.C under stirring4Stirring the PVDF resin for 3 hours to finally obtain the oil-resistant additive.
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 ethylene propylene diene monomer rubber
The composite material comprises a 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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 4mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 2.5g of styrene, 2.5g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 150 ℃ for 1.5h, and then reacting at 210 ℃ for 0.5 h;
(2) adding 6g of the product obtained in the step (1) into 2mg/mL aqueous acetic acid solution of chitosanDissolved in water to be composed of 1.68g of molecular weight 8 x 104The chitosan and acetic acid with the volume fraction of 5 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.48g of maleic anhydride, reacting at 50 deg.C for 7h, and slowly adding 0.8g of a polymer with a molecular weight of 30 x 10 at 65 deg.C under stirring4Stirring the PVDF resin for 3 hours to finally obtain the oil-resistant additive.
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, 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 tris (2, 4-di-tert-butylphenyl) phosphite.
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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 160 ℃ for 1.5 hours, and then reacting at 200 ℃ for 0.5 hour;
(2) adding 6g of the product obtained in the step (1) into 3mg/mL aqueous acetic acid solution of chitosan, wherein the molecular weight of the aqueous acetic acid solution of chitosan is 6 x 10 from 1.2g4The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 deg.C for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 40 x 10 at 60 deg.C under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
Comparative example 1
The difference from example 1 is that: in the preparation method of the oil-resistant auxiliary agent, Ti3C2TxTi in the dispersion3C2TxThe concentration of (2) was 0.5 mg/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, 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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding into tetrahydrofuran solution to obtain Ti with concentration of 0.5mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 160 ℃ for 1.5h, and then reacting at 200 ℃ for 0.5 h;
(2) adding 6g of the product obtained in the step (1) into 3mg/mL aqueous acetic acid solution of chitosan, wherein the molecular weight of the aqueous acetic acid solution of chitosan is 6 x 10 from 1.2g4The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 deg.C for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 40 x 10 at 60 deg.C under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
Comparative example 2
The difference from example 1 is that: in the preparation method of the oil-resistant assistant, the concentration of chitosan in acetic acid aqueous solution of chitosan is 6 mg/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, 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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 160 ℃ for 1.5h, and then reacting at 200 ℃ for 0.5 h;
(2) adding 6g of the product obtained in the step (1) into an acetic acid aqueous solution of chitosan with the concentration of 6mg/mL, wherein the acetic acid aqueous solution of chitosan is composed of 1.2g of chitosan with the molecular weight of 6 x 104The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 deg.C for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 40 x 10 at 60 deg.C under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
Comparative example 3
The difference from example 1 is that: in the preparation method of the oil-resistant additive, the molecular weight of the chitosan is 18 x 104。
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, 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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 160 ℃ for 1.5 hours, and then reacting at 200 ℃ for 0.5 hour;
(2) adding 6g of the product obtained in the step (1) into 3mg/mL aqueous acetic acid solution of chitosan, wherein the molecular weight of the aqueous acetic acid solution of chitosan is 18 x 10 from 1.2g4The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 deg.C for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 40 x 10 at 60 deg.C under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
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 104。
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, 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 200 kg/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 auxiliary agent comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL3C2TxAdding 1.5g acrylamide into the dispersion, stirring, adding 3g benzeneCarrying out polymerization reaction on a mixed solution of ethylene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, firstly reacting at 160 ℃ for 1.5h, and then reacting at 200 ℃ for 0.5 h;
(2) adding 6g of the product obtained in the step (1) into 3mg/mL aqueous acetic acid solution of chitosan, wherein the molecular weight of the aqueous acetic acid solution of chitosan is 6 x 10 from 1.2g4The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 deg.C for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 80 x 10 at 60 deg.C under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
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 104。
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 200 kg/mol; the monomer resin is aromatic monomer resin with molecular weight of 7000 and glass transition temperature of 130 ℃.
The preparation method of the oil-resistant additive comprises the following steps:
(1) 50mg of Ti3C2TxAdding the solution into tetrahydrofuran solution to prepare Ti with the concentration of 5mg/mL3C2TxAdding 1.5g of acrylamide into the dispersion, stirring, adding a mixed solution containing 3g of styrene, 3g of acrylonitrile, 0.2g of tert-dodecyl mercaptan and 20mL of ethanol, carrying out polymerization reaction, firstly reacting at 160 ℃ for 1.5h, and then reacting at 200 ℃ for 0.5 h;
(2) adding 6g of the product obtained in the step (1) into 3mg/mL aqueous acetic acid solution of chitosan, wherein the molecular weight of the aqueous acetic acid solution of chitosan is 6 x by 1.2g104The chitosan and acetic acid with the volume fraction of 7 percent are prepared; stirring the mixed solution, adding 0.1g of di-tert-butyl peroxide and 0.35g of maleic anhydride, reacting at 55 ℃ for 6h, and slowly adding 0.8g of a polymer with a molecular weight of 40 x 10 at 60 ℃ under stirring4Stirring the PVDF resin for 4 hours to finally obtain the oil-resistant additive.
Performance testing
Tensile strength and elongation at break: testing according to the standard GB/T2951;
tensile strength change rate and elongation at break change rate: after immersion in gasoline for 20h at a temperature of 23 ℃ the test was carried out according to the standard GB/T2951.
TABLE 1 Performance test results for gasoline resistant TPE materials
According to the performance test results in table 1, the gasoline-resistant TPE materials obtained in examples 1-4 completely meet the gasoline resistance requirement, and have excellent elasticity, mechanical properties and stability. Combining example 1 and comparative example 1, Ti3C2TxToo high a concentration in the dispersion tends to cause agglomeration due to its high surface energy, affecting the binding with other components, and reducing the mechanical properties of the TPE material. By combining the example 1 and the comparative examples 2 to 3, too high viscosity and poor dispersibility can be caused when the chitosan concentration is too high or the molecular weight is too high, the chitosan molecular chain is easily changed from a stretched chain structure to an intertwined coil structure, the reaction is not facilitated to carry out graft crosslinking, and the mechanical property and the oil resistance are reduced after the stability of the oil-resistant auxiliary agent is reduced. When the concentration of chitosan is too low, the content of hydroxyl groups and amino groups decreases, resulting in a decrease in oil resistance, a deterioration in compatibility with the matrix, and a deterioration in synergistic stability with PVDF resin. By combining the embodiment 1 and the comparative examples 4 to 5, the PVDF resin has higher viscosity as the molecular weight is higher, and is easy to form agglomeration and swelling when added, so that the dispersibility in a mixture is poor, and the mechanical property is reduced; and the PVDF resin has a single molecular chain at a lower molecular weightThe amount of fluorine 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 if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
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.
2. The gasoline-resistant TPE material of claim 1 wherein the weight portion of the SEBS rubber is greater than the total weight portion of the ethylene propylene diene monomer rubber and the polyethylene octene co-elastomer, and the weight portions of the ethylene propylene diene monomer rubber and the polyethylene octene co-elastomer are the same.
3. The gasoline-resistant TPE material of claim 1, wherein the polyethylene octene co-elastomer contains 30-50% of ethylene structural units and 50-70% of octene structural units; the weight average molecular weight of the polyethylene octene co-elastomer is 100-300 kg/mol.
4. The gasoline-resistant TPE material as claimed in claim 1, wherein the monomer resin is aromatic monomer resin or aliphatic monomer resin with molecular weight of 2000-10000.
5. The gasoline-resistant TPE material of claim 4, wherein the glass transition temperature of the aromatic monomer resin or the aliphatic monomer resin is 90-150 ℃.
6. The gasoline-resistant TPE material of claim 1, further comprising 1-3 parts of filler and 0.1-0.8 part of antioxidant.
7. The gasoline-resistant TPE material of claim 6 wherein the filler is carbon black, white carbon, silica, calcium carbonate or montmorillonite; the antioxidant is one or more of a phenol antioxidant and a phosphite antioxidant.
8. The gasoline-resistant TPE material of claim 1, wherein the preparation method of the oil-resistant auxiliary agent comprises the following steps:
(1) mixing Ti3C2TxPreparing Ti in tetrahydrofuran solution3C2TxAdding acrylamide into the dispersion liquid, stirring, adding a mixed solution containing styrene, acrylonitrile, tert-dodecyl mercaptan and ethanol, and performing polymerization reaction; the Ti3C2TxAnd the mass ratio of acrylamide to styrene to acrylonitrile is 0.1-1: 10-20: 25-40: 25-40;
(2) adding the substance obtained in the step (1) into an acetic acid aqueous solution of chitosan, stirring, 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 substance obtained in the step (1) to the chitosan to the maleic anhydride to the PVDF resin is 20-40: 5-9: 1-3: and 2-5, finally obtaining the oil-resistant assistant.
9. The gasoline-resistant TPE material of claim 1, wherein in step (1), the Ti is added3C2TxTi in the dispersion3C2TxThe concentration of (a) is 2-6 mg/mL; the polymerization reaction is as follows: the reaction is carried out for 1-2 h at a temperature of 150-170 ℃ and then for 0.5-1 h at a temperature of 180-220 ℃.
10. The gasoline-resistant TPE material as claimed in claim 1, wherein in the step (2), the concentration of the chitosan in the acetic acid aqueous solution of the chitosan is 1-4 mg/mL, and the volume fraction of the acetic acid is 3-10%; the chitosan has a molecular weight of 2 x 104~10*104(ii) a The reaction is carried out at 30-60 ℃ for 5-8 h; the molecular weight of the PVDF resin is 30 x 104~60*104(ii) a The heating and stirring are carried out for 2-4 h at 50-70 ℃.
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