CN114507381A - Thermal-oxidative-aging-resistant composite, preparation method thereof, polypropylene composition and polypropylene composite - Google Patents
Thermal-oxidative-aging-resistant composite, preparation method thereof, polypropylene composition and polypropylene composite Download PDFInfo
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Abstract
The invention relates to the technical field of antioxidants and preparation thereof, in particular to a thermal-oxidative-aging-resistant compound, a preparation method thereof and a polypropylene material, wherein the thermal-oxidative-aging-resistant compound comprises a core body, a first coating layer coated on the surface of the core body and a second coating layer coated on the surface of the first coating layer; the core body is a mixture which takes zirconium hydrogen phosphate as a carrier and is loaded with an antioxidant, the first coating layer is a layer formed by polysiloxane quaternary ammonium salt, and the second coating layer is a layer formed by long-chain alkyl ether potassium salt. The thermal-oxidative-aging-resistant compound provided by the invention has good storage and use stability, can generate excellent thermal-oxidative-aging-resistant effect on coal-made polypropylene, and can improve the mechanical property of the coal-made polypropylene.
Description
Technical Field
The invention relates to the technical field of antioxidants and preparation thereof, in particular to a thermal-oxidative-aging-resistant compound and a preparation method thereof, a polypropylene material and a polypropylene material.
Background
Coal-based polypropylene has the advantages of light weight, good and balanced mechanical properties, lower cost than petroleum-based polypropylene, basically equivalent performance to petroleum-based polypropylene and the like, and is widely applied to automobiles, household electrical appliances, building materials and various daily products. However, polypropylene has thermally unstable tertiary carbon groups, which are highly susceptible to heat and oxygen during thermal processing and long-term outdoor use to generate unstable allyl radicals, thereby initiating continuous cleavage and degradation of polypropylene molecular chains. The coal-made polypropylene is more complex than petroleum cracking olefin in the synthesis raw material component because the synthesis raw material of the coal-made polypropylene is from the coal-made olefin, so that the coal-made polypropylene is more sensitive to heat and oxygen. Therefore, the development of the special efficient and long-acting thermal-oxidative-aging-resistant composite auxiliary agent system for the coal-made polypropylene has important practical significance when being applied to the long-acting thermal-oxidative-aging-resistant high-performance coal-made polypropylene composite.
CN109762245A discloses a polypropylene material with long-term thermal-oxidative aging resistance, which is prepared by compounding polypropylene and high-crystallinity polyketone and adding a hindered amine light stabilizer and a metal purifying agent, and can effectively improve the long-term thermal-oxidative aging resistance of the polypropylene.
CN112409688A discloses a long-term thermal-oxidative-aging-resistant heat-resistant PP composite material and a preparation method thereof, wherein a hindered phenol main antioxidant GA-80 and a phosphite ester or thioester auxiliary antioxidant are added into polypropylene, so that the thermal-oxidative-aging-resistant performance and the heat resistance of the polypropylene are both improved.
Although antioxidants in the prior art can improve the long-term thermal-oxidative aging resistance of traditional polypropylene, the antioxidants have limited effect when applied to coal-made polypropylene which is more susceptible to thermal-oxidative aging, and the antioxidants with medium and small molecular weights directly added into polypropylene can cause outward migration and precipitation in the using process of products, thereby affecting the improvement of the long-term thermal-oxidative aging resistance of polypropylene products.
Therefore, there is a need to develop a high-efficiency and long-acting thermal-oxidative-aging-resistant composite antioxidant additive system specially for coal-made polypropylene to improve the long-term thermal oxidative aging resistance of the coal-made polypropylene and meet the stability of the coal-made polypropylene in thermal processing and the long-term use requirement of the product thereof.
Disclosure of Invention
The invention aims to solve the problems that an antioxidant in the prior art has limited effect on coal-made polypropylene and is easy to precipitate from the coal-made polypropylene, and provides a thermal-oxidative aging-resistant compound, a preparation method thereof and a polypropylene material.
In order to achieve the above object, a first aspect of the present invention provides a thermal-oxidative-aging-resistant composite comprising a core body, a first coating layer coated on a surface of the core body, and a second coating layer coated on a surface of the first coating layer; the core body is a mixture which takes zirconium hydrogen phosphate as a carrier and is loaded with an antioxidant, the first coating layer is a layer formed by polysiloxane quaternary ammonium salt, and the second coating layer is a layer formed by long-chain alkyl ether sylvite.
In a second aspect, the present invention provides a method of making a thermo-oxidative aging resistant composite, the method comprising:
(1) under the vacuum condition and in the presence of a first solvent, mixing an antioxidant with zirconium hydrogen phosphate powder, performing first aging, and drying a product obtained by the first aging to obtain composite powder;
(2) in the presence of a second solvent, mixing the composite powder with polysiloxane quaternary ammonium salt, and performing second aging to obtain a precursor;
(3) and (3) contacting the precursor with a long-chain alkyl ether potassium salt solution for reaction to obtain the thermal-oxidative-aging-resistant compound.
In a third aspect, the present invention provides a thermo-oxidative aging resistant composite prepared according to the method of the second aspect.
In a fourth aspect, the present invention provides a polypropylene material, which comprises coal-made polypropylene and an auxiliary agent, wherein the auxiliary agent is the thermal-oxidative-aging-resistant compound according to the first aspect or the third aspect.
In a fifth aspect, the present invention provides a polypropylene composite, which is obtained by melting, extruding and granulating the polypropylene material according to the fourth aspect.
Through the technical scheme, the invention has the following effects:
(1) the antioxidant is loaded in the zirconium hydrogen phosphate layered inorganic mesoporous material, so that the antioxidant can be uniformly released in the long-term use process of the polypropylene product, the long-acting thermal-oxidative aging resistance of the coal-based polypropylene is improved, and the defect that the long-acting thermal-oxidative aging resistance of the polypropylene is poor due to the fact that the micromolecule antioxidant is easy to separate out of the polypropylene is overcome;
(2) because the zirconium hydrogen phosphate layered inorganic mesoporous material has an acid absorption function, the oxygen scavenger can generate a synergistic interaction effect under the condition of not additionally adding an acid absorbent, the long-term thermal-oxidative aging resistance of the coal-made polypropylene is further improved, in addition, the zirconium hydrogen phosphate can also play a heterogeneous nucleation role, the crystallization of the polypropylene is promoted, the spherulite size is reduced, and the mechanical property of the polypropylene is improved;
(3) polysiloxane quaternary ammonium salt is used as an inner crown, long-chain alkyl ether potassium salt is used as an outer crown, and the antioxidant-loaded zirconium hydrogen phosphate layered inorganic mesoporous material is coated by a surface self-assembly technology and an ion exchange technology to obtain the ionic nanocomposite with the fluid-like characteristic, so that the thermal-oxidative aging resistant composite has good storage and use stability and can generate excellent thermal-oxidative aging resistant effect on polypropylene prepared from coal.
Drawings
FIG. 1 is an SEM photograph of antioxidant-loaded zirconium hydrogen phosphate of example 1 of the present invention;
FIG. 2 is a TEM image of a compound having resistance to thermal-oxidative aging, obtained in example 1 of the present invention;
FIG. 3A is a digital photograph of antioxidant-loaded zirconium hydrogen phosphate;
FIG. 3B is a digital photograph of a thermal-oxidative-aging-resistant composite;
FIG. 4A is a photograph of a pure coal-made polypropylene by a polarizing microscope;
FIG. 4B is a polarization microscope photograph of the coal-based polypropylene material in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously described, the present invention provides in a first aspect a thermal-oxidative-aging-resistant composite comprising a core, a first coating layer coated on a surface of the core, and a second coating layer coated on a surface of the first coating layer; the core body is a mixture which takes zirconium hydrogen phosphate as a carrier and is loaded with an antioxidant, the first coating layer is a layer formed by polysiloxane quaternary ammonium salt, and the second coating layer is a layer formed by long-chain alkyl ether sylvite.
According to the invention, the polysiloxane quaternary ammonium salt and the long-chain alkyl ether potassium salt can perform ion exchange and surface self-assembly to form a double-coating structure with the polysiloxane quaternary ammonium salt as an inner crown (a first coating layer) and the long-chain alkyl ether potassium salt as an outer crown (a second coating layer), so that the thermal-oxidative-aging-resistant compound has a fluid-like characteristic; the thermal-oxidative-aging-resistant compound with the structure has the following effects that firstly, double coating can protect the antioxidant loaded in the zirconium hydrogen phosphate mesoporous from leakage and loss in the storage and use processes, and the compound has good storage and use stability; secondly, the heat and oxygen aging resistant compound in a fluid-like form can be rapidly fused with a polypropylene melt in the melting process of polypropylene, so that a nucleus body is rapidly released, and excellent heat and oxygen aging resistant performance is generated; thirdly, the heat-oxygen aging resistant compound in the fluid-like form can be more uniformly dispersed or even dispersed in polypropylene in a monodisperse form, which is beneficial to uniform release of nucleus bodies in a polypropylene matrix and plays a more excellent heat-oxygen aging resistant role, and simultaneously, the nucleus bodies (antioxidant-loaded zirconium hydrogen phosphate) can fully play a heterogeneous nucleation role, so that the crystallization of the polypropylene is promoted, the spherulite size is reduced, and the mechanical property of the polypropylene is improved.
In some preferred embodiments of the present invention, in order to optimize the resistance of the thermal oxidative aging resistant composite to polypropylene against thermal oxidative aging, the weight ratio of the antioxidant, the zirconium hydrogen phosphate, the quaternary ammonium polysiloxane salt, and the potassium long-chain alkyl ether salt in the thermal oxidative aging resistant composite is 100: 10-25: 5-20: 10-30, preferably 100: 15-20: 15-18: 20-25.
In some preferred embodiments of the present invention, the antioxidant is selected from at least one of hindered phenolic antioxidants, phosphite antioxidants, and carbon radical trapping antioxidants.
Further preferably, the antioxidant comprises, based on the total weight of the antioxidant: 30-60 wt% of hindered phenol antioxidant, 30-60 wt% of phosphite antioxidant and 10-20 wt% of carbon free radical capture type antioxidant; the antioxidant preferably comprises: 45-60 wt% of hindered phenol antioxidant, 30-40 wt% of phosphite antioxidant and 10-15 wt% of carbon free radical capture type antioxidant. Under the optimal conditions, the ternary composite antioxidant system of the hindered phenol type antioxidant, the phosphite type antioxidant and the carbon free radical trapping type antioxidant can effectively weaken and block the polypropylene molecular chain fracture and degradation caused by oxygen free radicals, and can also capture and quench the carbon free radicals from the initial decomposition stage of the polypropylene which is heated to generate the carbon free radicals, so that the thermal oxidation aging decomposition path of the polypropylene is fundamentally blocked. Compared with the traditional main and auxiliary binary composite antioxidant systems, the ternary composite antioxidant system has more excellent thermal-oxidative-aging-resistant efficacy, and is particularly suitable for thermal-oxidative-aging-resistant modification and processing of coal-made polypropylene with thermal-oxidative-aging resistance inferior to that of the traditional petroleum-based polypropylene.
According to the invention, under the preferable conditions, the hindered phenol antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 3114 and antioxidant 2246; further preferably, the phosphite antioxidant is at least one selected from the group consisting of antioxidant 168, antioxidant 398, antioxidant 626 and antioxidant 852; more preferably, the carbon radical trapping antioxidant is at least one selected from the group consisting of antioxidant HP-136, antioxidant Revonox 501 and antioxidant Revonox 394.
In some preferred embodiments of the invention, the silicone quaternary ammonium salt is selected from dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride; preferably, the long chain alkyl ether potassium salt is selected from poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt.
According to the invention, under a preferable condition, the zirconium hydrogen phosphate is particles with a layered structure and mesopores, and the particle diameter of the particles is 1-10 μm; under the preferable conditions, the antioxidant can be loaded in the mesopores of the zirconium hydrogen phosphate, so that the small molecular antioxidant is prevented from being separated out from the polypropylene, and the thermal-oxidative aging resistant compound is uniformly released in the polypropylene for a long time.
In a second aspect, the present invention provides a method of making a thermo-oxidative aging resistant composite, wherein the method comprises:
(1) under the vacuum condition and in the presence of a first solvent, mixing an antioxidant with zirconium hydrogen phosphate powder, performing first aging, and drying a product obtained by the first aging to obtain composite powder;
(2) in the presence of a second solvent, mixing the composite powder with polysiloxane quaternary ammonium salt, and performing second aging to obtain a precursor;
(3) and (3) contacting the precursor with a long-chain alkyl ether potassium salt solution for reaction to obtain the thermal-oxidative-aging-resistant compound.
According to the invention, under the preferable conditions, in the step (1), the weight ratio of the antioxidant to the zirconium hydrogen phosphate powder is 100: 10-25, for example 100: 10. 100, and (2) a step of: 12. 100, and (2) a step of: 14. 100, and (2) a step of: 16. 100, and (2) a step of: 18. 100, and (2) a step of: 20. 100, and (2) a step of: 22. 100, and (2) a step of: 25 or any two of the above ratios, preferably 100: 15-20, and under the preferable conditions, the oxidation resistance of the thermal-oxidative-aging-resistant compound to coal-made polypropylene can be optimized.
According to the present invention, preferably, the antioxidant is used in an amount of 100 g: 20-50 mL; further preferably, the first solvent is selected from a polar solvent, preferably acetone or tetrahydrofuran; under the above preferred conditions, the antioxidant can be completely dissolved and a uniform solution can be formed.
According to the present invention, preferably, the conditions of the first aging include: the pressure is-75 kPa to-70 kPa, and the time is 3 to 5 hours; the antioxidant can be fully absorbed by the zirconium hydrogen phosphate through the first aging, and the loading capacity of the antioxidant is improved.
According to the present invention, preferably, the antioxidant is selected from at least one of hindered phenol-based antioxidants, phosphite-based antioxidants, and carbon radical trapping-type antioxidants; further preferably, the antioxidant comprises, based on the total weight of the antioxidant: 30-60 wt% of hindered phenol antioxidant, 30-60 wt% of phosphite antioxidant and 10-20 wt% of carbon free radical capture type antioxidant; more preferably, the antioxidant comprises, based on the total weight of the antioxidant: 45-60 wt% of hindered phenol antioxidant, 30-40 wt% of phosphite antioxidant and 10-15 wt% of carbon free radical capture type antioxidant.
Further preferably, the hindered phenol antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 3114 and antioxidant 2246; further preferably, the phosphite antioxidant is at least one selected from the group consisting of antioxidant 168, antioxidant 398, antioxidant 626 and antioxidant 852; more preferably, the carbon radical trapping antioxidant is at least one selected from the group consisting of antioxidant HP-136, antioxidant Revonox 501 and antioxidant Revonox 394.
According to the present invention, preferably, the method further comprises: drying the product obtained by the first aging, wherein the drying conditions comprise: the temperature is 60-80 ℃, and the time is 1-3 h; by drying, the antioxidant can be retained in the zirconium hydrogen phosphate mesopores and between the layers, and a core body (composite powder) loaded with the antioxidant and having zirconium hydrogen phosphate as a carrier can be obtained.
In some preferred embodiments of the invention, in step (2), carboxyl groups in the zirconium hydrogen phosphate can react with silicon hydroxyl groups in the polysiloxane quaternary ammonium salt, so that the polysiloxane quaternary ammonium salt is grafted to the surface of the zirconium hydrogen phosphate through chemical bonds, and then the second aging process is performed, so that the polysiloxane quaternary ammonium salt can be sufficiently coated on the surface of the composite powder, that is, the surface of the core body is coated with the first coating layer, so as to obtain a precursor; preferably, the weight ratio of the composite powder to the polysiloxane quaternary ammonium salt is 100: 5-20, which may be, for example, 100: 5. 100, and (2) a step of: 8. 100, and (2) a step of: 10. 100, and (2) a step of: 12. 100, and (2) a step of: 15. 100, and (2) a step of: 18. 100, and (2) a step of: 20 or any two of the above ratios, preferably 10 to 15.
According to the present invention, preferably, the amount of the composite powder and the second solvent is in a relationship of 100 g: 150-; further preferably, the second solvent is water.
According to the present invention, preferably, the conditions of the second aging include: the temperature is 20-30 ℃ and the time is 12-48 h.
According to the present invention, preferably, the method further comprises: and drying the product obtained by the second aging, wherein the drying conditions comprise: the temperature is 100-120 ℃, and the time is 12-48 h.
In some preferred embodiments of the present invention, in step (3), the polysiloxane quaternary ammonium salt can be ion-exchanged with the long-chain alkyl ether potassium salt, so as to form a second coating layer on the surface of the precursor. Preferably, the concentration of the long-chain alkyl ether potassium salt in the long-chain alkyl ether potassium salt solution is 5 to 20 wt%, and may be, for example, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, or any value in the range of any two of the above values, and is preferably 8 to 12 wt%; further preferably, in the step (3), the dosage relationship between the precursor and the long-chain alkyl ether potassium salt solution is 100 g: 150 and 250 mL.
In the present invention, preferably, in the step (3), the reaction is performed under stirring conditions, and further preferably, the reaction conditions include: the temperature is 50-100 ℃ and the time is 12-48 h.
According to a particularly preferred embodiment of the invention, the method for preparing said thermo-oxidative ageing-resistant composite comprises:
(1) dissolving an antioxidant in a polar solvent to obtain an antioxidant solution, wherein the dosage relationship of the antioxidant and the first solvent is 100 g: 20-50 mL;
adding zirconium hydrogen phosphate powder into the antioxidant solution, then performing first aging for 3-5h under the conditions that the vacuum degree is-75 kPa to-70 kPa and the temperature is 20-30 ℃, and then drying for 1-3h under the vacuum condition at 60-80 ℃ to completely volatilize the polar solvent to obtain composite powder;
wherein the weight ratio of the antioxidant to the zirconium hydrogen phosphate powder is 100: 15-20 parts of;
the antioxidant comprises, based on the total weight of the antioxidant: 45-60 wt% of hindered phenol antioxidant, 30-40 wt% of phosphite antioxidant and 10-15 wt% of carbon free radical capture type antioxidant;
(2) stirring the composite powder and dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in ionized water for 2-3h at 20-30 ℃, then performing secondary aging on the reaction mixture for 12-48h, washing the obtained product with the deionized water, filtering, and drying at 100-120 ℃ for 12-48h to obtain a precursor;
wherein the weight ratio of the composite powder to the polysiloxane quaternary ammonium salt is 100: 10-15 parts of; the dosage relationship of the composite powder and the deionized water is 100 g: 150-;
(3) mixing the precursor with poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt aqueous solution (5-20 wt%), stirring and reacting at 50-100 ℃ for 12-48h, washing the product with deionized water, filtering, and drying at 100-120 ℃ for 12-48h to obtain the thermal-oxidative aging-resistant compound;
the dosage relationship between the precursor and the long-chain alkyl ether sylvite solution is 100 g: 150 and 250 mL.
In a third aspect, the present invention provides a compound resistant to thermooxidative aging, prepared according to the method of the first aspect.
In a fourth aspect, the present invention provides a polypropylene material, which comprises coal-made polypropylene and an auxiliary agent, wherein the auxiliary agent is the thermal-oxidative-aging-resistant compound according to the first aspect or the third aspect.
According to the present invention, preferably, the polypropylene material comprises, based on the total amount of the polypropylene material: 97-99.7 wt% of coal-made polypropylene and 0.3-3 wt% of the thermal-oxidative aging resistant composite.
In the invention, the coal-made polypropylene is polypropylene produced by taking coal as a raw material, and the number average molecular weight of the coal-made polypropylene is 30000-120000 g/mol.
In a fifth aspect, the present invention provides a polypropylene composite, which is obtained by melting, extruding and granulating the polypropylene material according to the fourth aspect.
In a preferred embodiment of the present invention, the method for preparing the polypropylene composite comprises:
premixing a coal-made polypropylene base material and the thermal-oxidative aging resistant compound, and then carrying out melt extrusion blending, bracing and granulation on the premixed material in a double-screw extruder;
preferably, the temperature of the screw barrel is 190 ℃ to 230 ℃, and the screw rotating speed is controlled at 300 ℃ to 350 r/min.
In the invention, the thermal-oxidative-aging-resistant compound can be used as a single auxiliary agent to be directly compounded with polypropylene or used by being mixed with other auxiliary agents, the dosage of the thermal-oxidative-aging-resistant compound and the types and dosages of other auxiliary agents can be correspondingly adjusted according to different actual requirements of the polypropylene compound, and the invention is not repeated herein.
The present invention will be described in detail below by way of examples.
In the following examples, zirconium hydrogen phosphate powder was obtained from Mianzhuo chemical Co., Ltd.
The coal-made polypropylene is the coal-made homopolymerized polypropylene with the brand number of 1102K produced by Ningxia coal industry Limited liability company of the national energy group.
Preparation example 1
(1) Dissolving 45g of antioxidant 1010, 40g of antioxidant 168 and 15g of antioxidant HP-136 in 30mL of acetone to obtain an antioxidant solution;
adding 15g of zirconium hydrogen phosphate powder into an antioxidant solution, then carrying out first aging for 4h at 25 ℃ and a vacuum degree of-75 kPa, and then drying for 2h at 70 ℃ in a vacuum oven to obtain composite powder (a core body);
(2) stirring the composite powder and 15g of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in 200mL of ionized water for 3h at 25 ℃, then carrying out secondary aging on the reaction mixture for 20h, washing the obtained product with deionized water, filtering, and drying at 105 ℃ for 24h to obtain a precursor;
(3) the precursor is mixed with 220mL of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt aqueous solution (10 wt%), stirred at 70 ℃ for reaction for 24 hours, and then the product is washed by deionized water, filtered and dried at 105 ℃ for 24 hours, wherein the specific dosage of each substance is shown in Table 1, and the thermal-oxidative-aging-resistant compound A-1 is obtained.
Preparation example 2
(1) Dissolving 50g of antioxidant 3114, 40g of antioxidant 168 and 10g of antioxidant Revonox 501 in 40mL of acetone to obtain an antioxidant solution;
adding 13g of zirconium hydrogen phosphate powder into an antioxidant solution, then carrying out first aging for 4h at 25 ℃ and a vacuum degree of-75 kPa, and then drying for 2h at 70 ℃ in a vacuum oven to obtain composite powder (a core body);
(2) stirring the composite powder and 14g of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in 200mL of ionized water for 3h at 25 ℃, then carrying out secondary aging on the reaction mixture for 20h, and then washing the obtained product with deionized water, filtering and drying at 105 ℃ for 24h to obtain a precursor;
(3) the precursor is mixed with 230mL of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt aqueous solution (10 wt%), stirred at 70 ℃ for reaction for 24 hours, and then the product is washed by deionized water, filtered and dried at 105 ℃ for 24 hours, wherein the specific dosage of each substance is shown in Table 1, and the thermal-oxidative-aging-resistant compound A-2 is obtained.
Preparation example 3
(1) Dissolving 60g of antioxidant 1010, 30g of antioxidant 168 and 10g of antioxidant Revonox 501 in 40mL of acetone to obtain an antioxidant solution;
adding 20g of zirconium hydrogen phosphate powder into an antioxidant solution, then carrying out first aging for 4h at 25 ℃ and a vacuum degree of-75 kPa, and then drying for 2h at 70 ℃ in a vacuum oven to obtain composite powder (a core body);
(2) stirring the composite powder and 16g of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in 200mL of ionized water for 3h at 25 ℃, then carrying out secondary aging on the reaction mixture for 20h, and then washing the obtained product with deionized water, filtering and drying at 105 ℃ for 24h to obtain a precursor;
(3) the precursor is mixed with 230mL of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt aqueous solution (10 wt%), stirred at 70 ℃ for reaction for 24 hours, and then the product is washed by deionized water, filtered and dried at 105 ℃ for 24 hours, wherein the specific dosage of each substance is shown in Table 1, so that the thermal-oxidative-aging-resistant compound A-3 is obtained.
Preparation example 4
(1) Dissolving 45g of antioxidant 1076, 35g of antioxidant 168 and 20g of antioxidant Revonox 394 in 25mL of acetone to obtain an antioxidant solution;
adding 18g of zirconium hydrogen phosphate powder into an antioxidant solution, then carrying out first aging for 3.5h at 25 ℃ and a vacuum degree of-75 kPa, and then drying for 2h at 70 ℃ in a vacuum oven to obtain composite powder (a core body);
(2) stirring the composite powder and 17g of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in 230mL of ionized water for 3h at 25 ℃, then carrying out secondary aging on the reaction mixture for 20h, and then washing the obtained product with the deionized water, filtering and drying at 105 ℃ for 24h to obtain a precursor;
(3) the precursor is mixed with 225mL of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt aqueous solution (10 wt%), stirred at 70 ℃ for reaction for 24 hours, and then the product is washed by deionized water, filtered and dried at 105 ℃ for 24 hours, wherein the specific dosage of each substance is shown in Table 1, so that the thermal-oxidative-aging-resistant compound A-4 is obtained.
Preparation example 5
(1) Dissolving 60g of antioxidant 1010, 30g of antioxidant 168 and 10g of antioxidant Revonox 501 in 40mL of acetone to obtain an antioxidant solution;
adding 20g of zirconium hydrogen phosphate powder into an antioxidant solution, then performing first aging for 4 hours at 25 ℃ under a vacuum degree of-75 kPa, and then drying for 2 hours at 70 ℃ in a vacuum oven to obtain composite powder (a core body);
(2) stirring the composite powder and 16g of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in 200mL of ionized water for 3h at 25 ℃, then carrying out secondary aging on the reaction mixture for 20h, and then washing the obtained product with deionized water, filtering and drying at 105 ℃ for 24h to obtain a precursor;
(3) the precursor is mixed with 225mL of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt aqueous solution (10 wt%), then stirred at 70 ℃ for 24 hours, and the product is washed by deionized water, filtered and dried at 105 ℃ for 24 hours, wherein the specific dosage of each substance is shown in Table 1, so as to obtain the thermal-oxidative-aging-resistant compound A-5.
Preparation example 6
According to the method of preparation example 5 except that zirconium hydrogenphosphate powder was used in an amount of 10g, the concrete amounts of each material are shown in Table 1, compound A-6 was obtained which was resistant to thermal oxidative aging.
Preparation example 7
According to the method of preparation example 5 except that the amount of zirconium hydrogenphosphate powder was 25g and the specific amounts of the respective substances were as shown in Table 1, compound A-7 was obtained as a heat-oxygen aging resistant compound.
Preparation example 8
According to the method of preparation example 5 except that 5g of dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride was used in the amounts shown in Table 1, compound A-8 was obtained.
Preparation example 9
According to the method of preparation example 5 except that 20g of dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride was used, the specific amounts of the respective substances are shown in Table 1, thermal oxidative aging resistant composite A-9 was obtained.
Preparation example 10
According to the method of preparation example 5 except that the amount of the aqueous solution (10% by weight) of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt used was 100mL, the specific amounts of the respective substances are shown in Table 1, and the specific amounts of the respective substances are shown in Table 1, thermal oxidative aging resistant composite A-10 was obtained.
Preparation example 11
The procedure of preparation example 5 was followed except that an aqueous solution (10% by weight) of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt was used in an amount of 300mL to obtain thermal-oxidative-aging-resistant complex A-11.
Preparation examples 12 to 15
Hindered phenol antioxidant, phosphite ester antioxidant and carbon free radical capture antioxidant are directly mixed, and the specific dosage is shown in table 1, so as to obtain thermal-oxidative-aging-resistant compounds B-1 to B-4.
Preparation example 16
The process of preparation 5 was followed, except that the antioxidant consisted of: 60g of antioxidant 1010 and 40g of antioxidant 168, wherein the specific dosage of each substance is shown in Table 1, and the thermal-oxidative-aging-resistant compound B-5 is obtained.
Preparation example 17
The process of preparation 5 was followed, except that the antioxidant consisted of: and obtaining the compound B-6 with thermal-oxidative aging resistance by using 1010 g of antioxidant and 40g of Revonox 501 antioxidant.
Preparation example 18
The process of preparation 5 was followed, except that the antioxidant consisted of: 60g of antioxidant 168 and 40g of antioxidant Revonox 501, the specific dosage of each substance is shown in Table 1, and the compound B-7 with resistance to thermal oxidative aging is obtained.
Preparation example 19
According to the method of preparation example 5, except that step (2) was not included, i.e., the composite powder obtained in step (1) was not coated with dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride, the specific amounts of the respective substances were as shown in Table 1, to obtain a thermal-oxidative-aging-resistant composite B-8.
Preparation example 20
According to the method of preparation example 5, except that step (3) was not included, i.e., the precursor prepared in step (2) was not coated with poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt, the specific amounts of each substance were as shown in Table 1, to obtain thermal oxidative aging resistant composite B-9.
TABLE 1
TABLE 1 continuation
Note: quaternary ammonium salt refers to dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride;
potassium salt means an aqueous solution of poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt at a mass concentration of 10 wt%.
Examples 1 to 11 and comparative examples 1 to 11
Preparation of polypropylene composite:
uniformly mixing the thermal-oxidative-aging-resistant compound prepared from the thermal-oxidative-aging-resistant compounds A-1 to A-11 and the thermal-oxidative-aging-resistant compounds B-1 to B-11 with the coal-made polypropylene in a high-speed mixer, feeding the mixture into a double-screw extrusion granulator set through a conical feeding machine, and performing melt extrusion and granulation to obtain a polypropylene compound; the screw rotation speed of the twin-screw extruder was set at 320 rpm, the barrel temperature was segmented at 190-.
FIG. 1 is an SEM image of antioxidant-supported zirconium hydrogen phosphate of example 1 of the present invention, and it can be seen from FIG. 1 that the zirconium hydrogen phosphate used in the examples has a regular layered nanostructure.
FIG. 2 is a TEM image of a compound having resistance to thermal-oxidative aging, obtained in example 1 of the present invention; as is clear from fig. 2, the zirconium hydrogen phosphate surface has a coating.
FIG. 3 is a digital photograph of antioxidant-loaded zirconium hydrogen phosphate and a digital photograph of a thermal-oxidative aging-resistant composite; as can be seen from fig. 3A, the uncoated zirconium hydrogen phosphate is in the form of a solid powder; as can be seen in fig. 3B, the resulting thermal-oxidative-aging-resistant composite after coating has macroscopic fluid-like characteristics.
FIG. 4A is a polarization microscope photograph of a pure coal-based polypropylene, and FIG. 4A is a polarization microscope photograph of a coal-based polypropylene material in example 1 of the present invention; as can be seen from FIG. 4A, the pure coal-made polypropylene has large-sized spherulites, while the spherulites of the polypropylene added with the thermo-oxidative aging resistant compound in FIG. 4B are significantly reduced in size, indicating the effectiveness of heterogeneous nucleation.
Test example
The oxidation induction time at 200 ℃ is measured by adopting the Chinese national standard GB/T19466.6-2009;
the oxidation induction temperature is measured by adopting the Chinese national standard GB/T19466.6-2009;
the tensile strength is measured by adopting the Chinese national standard GB/T1040-92;
the elongation at break is measured by adopting the Chinese national standard GB/T1040-92;
the notch impact strength is measured by adopting the Chinese national standard GB/T1043.1-2008;
the retention rate of tensile strength after 500-hour accelerated aging experiments at 150 ℃ is measured by adopting Chinese national standard GB/T19466.6-2009;
the retention rate of the elongation at break after the accelerated aging test at 150 ℃ for 500 hours is measured by adopting the Chinese national standard GB/T19466.6-2009.
TABLE 2
As can be seen from Table 2, the oxidation induction time and temperature at 200 ℃ of the polypropylene composites prepared in examples 1-5 are significantly higher than those of the polypropylene composites prepared in comparative examples 1-5, which shows that the thermal oxidation aging resistance and long-term thermal oxidation aging resistance of the coal-made polypropylene can be significantly improved by using the thermal oxidation aging resistance composite prepared in the examples of the present invention under the condition that the antioxidant components and the compounding ratio are completely the same.
In addition, the mechanical property test results also show that the tensile strength, the elongation at break, the notch impact strength, and the retention rate of the tensile strength after aging and the retention rate of the elongation at break of the polypropylene composites prepared in examples 1 to 5 are all obviously higher than those of the polypropylene composites of comparative examples 1 to 5, which shows that the polypropylene composites prepared in the examples of the invention have better strength and toughness. Therefore, the technology of the invention has the double effects of improving the long-term thermal-oxidative aging resistance and the mechanical property of the polypropylene, which are not possessed by the traditional technology at present.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A thermal oxidative aging resistant composite comprising a core, a first coating layer coated on a surface of the core, and a second coating layer coated on a surface of the first coating layer; the core body is a mixture which takes zirconium hydrogen phosphate as a carrier and is loaded with an antioxidant, the first coating layer is a layer formed by polysiloxane quaternary ammonium salt, and the second coating layer is a layer formed by long-chain alkyl ether sylvite.
2. The anti-thermo-oxidative aging compound according to claim 1, wherein the weight ratio of the antioxidant, the zirconium hydrogen phosphate, the silicone quaternary ammonium salt, and the long chain alkyl ether potassium salt in the anti-thermo-oxidative aging compound is 100: 10-25: 5-20: 10-30, preferably 100: 15-20: 15-18: 20-25.
3. The anti-thermooxidative aging composite according to claim 1 or 2, wherein the antioxidant is selected from at least one of hindered phenolic antioxidants, phosphite antioxidants and carbon radical trapping antioxidants;
preferably, the antioxidant comprises, based on the total weight of the antioxidant: 30-60 wt% of hindered phenol antioxidant, 30-60 wt% of phosphite antioxidant and 10-20 wt% of carbon free radical capture type antioxidant;
preferably, the antioxidant comprises, based on the total weight of the antioxidant: 45-60 wt% of hindered phenol antioxidant, 30-40 wt% of phosphite antioxidant and 10-15 wt% of carbon free radical capture type antioxidant.
4. The anti-thermal-oxidative-aging compound according to claim 3, wherein the hindered phenolic antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 3114 and antioxidant 2246;
preferably, the phosphite antioxidant is at least one selected from the group consisting of antioxidant 168, antioxidant 398, antioxidant 626 and antioxidant 852;
preferably, the carbon radical capturing antioxidant is at least one selected from the group consisting of antioxidant HP-136, antioxidant Revonox 501 and antioxidant Revonox 394.
5. The thermal-oxidative-aging-resistant compound according to any one of claims 1 to 4, wherein the silicone quaternary ammonium salt is selected from dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride;
preferably, the long chain alkyl ether potassium salt is selected from poly (ethylene glycol) 4-nonylphenyl-3-thiopropyl ether potassium salt;
preferably, the zirconium hydrogen phosphate is a particle having a layered structure and mesopores, and the particle diameter is 1 to 10 μm.
6. A method of making a thermo-oxidative aging resistant composite, the method comprising:
(1) under the vacuum condition and in the presence of a first solvent, mixing an antioxidant with zirconium hydrogen phosphate powder, performing first aging, and drying a product obtained by the first aging to obtain composite powder;
(2) in the presence of a second solvent, mixing the composite powder with polysiloxane quaternary ammonium salt, and performing second aging to obtain a precursor;
(3) and (3) contacting the precursor with a long-chain alkyl ether potassium salt solution for reaction to obtain the thermal-oxidative-aging-resistant compound.
7. The method of claim 6, wherein in step (1), the weight ratio of the antioxidant to the zirconium hydrogen phosphate powder is 100: 10-25;
preferably, the dosage relationship between the antioxidant and the first solvent is 100 g: 20-50 mL;
preferably, the first solvent is selected from a polar solvent, preferably acetone or tetrahydrofuran;
preferably, the conditions of the first aging include: the pressure is-75 kPa to-70 kPa, and the time is 3 to 5 hours.
8. The method according to claim 6 or 7, wherein in step (2), the weight ratio of the composite powder to the silicone quaternary ammonium salt is 100: 5-20 parts of;
preferably, the amount of the composite powder and the second solvent is 100 g: 150-250 mL;
preferably, the second solvent is water;
preferably, the conditions of the second aging include: the temperature is 20-30 ℃ and the time is 12-48 h.
9. The method according to any one of claims 6 to 8, wherein in the step (3), the concentration of the long-chain alkyl ether potassium salt in the long-chain alkyl ether potassium salt solution is 5 to 20 wt%;
preferably, in the step (3), the dosage relationship between the precursor and the long-chain alkyl ether potassium salt solution is 100 g: 150-250 mL;
preferably, the conditions of the reaction include: the temperature is 50-100 ℃ and the time is 12-48 h.
10. A thermo-oxidative aging resistant composite prepared according to the method of any one of claims 6 to 9.
11. A polypropylene composition comprising a coal-based polypropylene and an auxiliary agent, wherein the auxiliary agent is the thermal-oxidative-aging-resistant composite according to any one of claims 1 to 5 and 10;
preferably, the polypropylene composition comprises, based on the total amount of the polypropylene composition: 97-99.7 wt% of coal-made polypropylene and 0.3-3 wt% of the thermal-oxidative aging resistant composite;
preferably, the number average molecular weight of the coal-made polypropylene is 30000-120000 g/mol.
12. A polypropylene composite obtained by melting, extruding and pelletizing the polypropylene composition according to claim 11.
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