CN113024814B - Bio-based polysiloxane scratch-resistant auxiliary agent, preparation method thereof and scratch-resistant composite material - Google Patents

Bio-based polysiloxane scratch-resistant auxiliary agent, preparation method thereof and scratch-resistant composite material Download PDF

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CN113024814B
CN113024814B CN202110274249.1A CN202110274249A CN113024814B CN 113024814 B CN113024814 B CN 113024814B CN 202110274249 A CN202110274249 A CN 202110274249A CN 113024814 B CN113024814 B CN 113024814B
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冯建湘
彭思梅
刘跃军
罗林园
吴任钊
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Hunan University of Technology
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract

The invention relates to the technical field of scratch resistance, and provides a bio-based polysiloxane scratch resistance auxiliary agent, a preparation method thereof and a scratch resistance composite material. The invention utilizes green and renewable bio-based material derivatives to carry out modified grafting on low-hydrogen polysiloxane, and designs and synthesizes the bio-based polysiloxane scratch-resistant assistant. When the bio-based polysiloxane scratch-resistant auxiliary agent is used for a scratch-resistant composite material, the main chain of the bio-based polysiloxane scratch-resistant auxiliary agent can migrate to the surface of the composite material to form a layer of lubricating film in the process of forming a polymer substrate, so that the scratch resistance of the composite material is improved; the side chain of the rigid benzene ring structure can endow the polymer substrate with certain hardness and higher thermal property, and further improve the scratch resistance and precipitation stickiness resistance of the composite material. Experimental results show that the bio-based polysiloxane scratch-resistant auxiliary agent provided by the invention can obviously improve the scratch resistance of a polymer substrate; meanwhile, a step curve test further proves that the scratch resistance of the polymer substrate is obviously improved.

Description

Bio-based polysiloxane scratch-resistant auxiliary agent, preparation method thereof and scratch-resistant composite material
Technical Field
The invention relates to the technical field of scratch-resistant auxiliaries, in particular to a bio-based polysiloxane scratch-resistant auxiliary, a preparation method thereof and a scratch-resistant composite material.
Background
With the wide application of polymer materials in the fields of packaging, automobiles, architectural decoration and the like, the requirements on the surface quality of the polymer materials are higher and higher. In the processes of transportation, taking and placing, assembly, use and the like, the surface of the material is easily scratched by hard objects or sharp objects, so that the surface of the material is cracked or damaged in a brittle manner, and the attractiveness of the product is reduced; meanwhile, the scratches formed on the surface of the product are also easy to form stress concentration, so that the service performance of the material is reduced, and even the function failure of the product is caused.
At present, scholars at home and abroad make a great deal of research on the scratch resistance of polymer substrates, and the research roughly comprises the following aspects: 1) the scratch resistance of the substrate is improved by adjusting the crystallinity and the crystallization quality. However, the improvement of crystallinity can reduce the toughness of the material, and cannot meet the basic use requirements of application type plastics. 2) And coating a scratch-resistant protective coating on the surface of the polymer substrate. The method has high cost and is not environment-friendly. 3) The scratch modification of polymers is achieved by blending between different polymers. The improvement effect of the method is not obvious. 4) The surface friction coefficient of the base material is reduced by adding the scratch-resistant agent or the auxiliary agent, so that the scratch resistance of the base material is improved.
The principle of adding the scratch-resistant agent or the auxiliary agent to improve the scratch resistance of the polymer substrate is that polysiloxane migrates to the surface of the substrate to form a layer of lubricating film, so that the friction coefficient of the surface of the material is reduced, and the scratch resistance of the material is reduced. The method can improve the scratch resistance of the substrate, and has wide source of the additive and low cost. For example, the novel polysiloxane scratch resistant agent prepared by grafting olefin and allyl glycidyl ether on polymethylhydrosiloxane is prepared by Wangxiaohui and Meiqingran of south China university, and the scratch resistant polypropylene composite material prepared by adding the novel polysiloxane scratch resistant agent to polypropylene has been shown by the following research: compared with pure polypropylene, the scratch resistance of the novel polysiloxane polypropylene material is obviously improved. Although the novel polysiloxane has a remarkable effect on the scratch resistance of polypropylene, reactants of the novel scratch resistance agent are non-renewable non-green resources, and the trend of green development is violated. Therefore, the development of a novel environment-friendly polysiloxane scratch resistant agent and the preparation of a high polymer material with excellent scratch resistance meet the requirements of the market and the green development.
Disclosure of Invention
The invention aims to provide a bio-based polysiloxane scratch-resistant auxiliary agent, a preparation method thereof and a scratch-resistant composite material. The bio-based polysiloxane scratch-resistant auxiliary agent provided by the invention is green and environment-friendly, and can obviously improve the scratch resistance of a composite material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a bio-based polysiloxane scratch-resistant auxiliary agent, which has a structure shown in a formula (I) or a formula (II):
Figure BDA0002975913690000021
wherein a is 0,3,4,5,6,7 or 8; b is 0,1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765;
in the formula (II), b is 1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765;
in the formula (III), x and n respectively represent the composition parts of two structural units, wherein x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765.
The invention provides a preparation method of a bio-based polysiloxane scratch-resistant auxiliary agent in the technical scheme, which comprises the following steps:
(1) mixing hydrogenated cardanol, an alkaline catalyst, an organic solvent and halogenated olefin, and carrying out substitution reaction to obtain an intermediate;
(2) mixing the intermediate obtained in the step (1) with a catalyst, toluene and low hydrogen-containing polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (I);
or mixing the unhydrogenated cardanol with a catalyst, toluene and low hydrogen-containing polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (II);
or mixing the estragole with a catalyst, toluene and low hydrogen polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (III).
Preferably, the basic catalyst in step (1) comprises one or more of potassium hydroxide, sodium hydroxide and potassium carbonate.
Preferably, the halogenated olefin in step (1) comprises one or more of bromopropene, 8-bromo-1-octene, 7-bromo-1-heptene, 6-bromo-1-hexene, 5-bromo-1-pentene, 4-bromo-1-butene and chloropropene.
Preferably, the mass ratio of the hydrogenated cardanol, the basic catalyst and the halogenated olefin in the step (1) is (1-1.1): (1-1.2): (1-1.2).
Preferably, the temperature of the substitution reaction in the step (1) is 78-85 ℃, and the time of the substitution reaction is 7-10 h.
Preferably, the ratio of the intermediate to the amount of the catalyst and the low hydrogen polysiloxane in the step (2) is (10-14): (4.5X 10)-7～8.0×10-7)：(10～12)。
Preferably, the temperature of the hydrosilylation in the step (2) is 75-85 ℃, and the time of the hydrosilylation is 3.5-4.5 h.
The invention also provides a scratch-resistant composite material, which comprises a scratch-resistant auxiliary agent and a polymer substrate, wherein the scratch-resistant auxiliary agent is the bio-based polysiloxane scratch-resistant auxiliary agent in the technical scheme or the bio-based polysiloxane scratch-resistant auxiliary agent prepared by the preparation method in the technical scheme; the polymeric substrate comprises polypropylene, polycarbonate, polyamide, polymethyl methacrylate or acrylonitrile-butadiene-styrene plastic.
The invention provides a bio-based polysiloxane scratch-resistant auxiliary agent, which has a structure shown in a formula (I) or (II):
Figure BDA0002975913690000031
wherein a is 0,3,4,5,6,7 or 8; b is 0,1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765;
in the formula (II), b is 1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765;
in the formula (III), x and n respectively represent the composition parts of two structural units, wherein x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765. According to the invention, the low hydrogen-containing Polysiloxane (PMHS) is subjected to modified grafting by utilizing the green and renewable cardanol derivative, and the bio-based polysiloxane scratch-resistant auxiliary agent with the side chain containing a benzene ring structure and long-chain alkane is designed and synthesized. When the bio-based polysiloxane scratch-resistant auxiliary agent is used for a scratch-resistant composite material, the main chain of the bio-based polysiloxane scratch-resistant auxiliary agent can migrate to the surface of the composite material to form a layer of lubricating film in the process of forming a polymer substrate, so that the friction coefficient of the surface of the material is reduced, and the scratch-resistant performance of the composite material is improved; the side chain group containing the long chain can have good compatibility with a base material, and the phenomenon of separation and stickiness of the material in the long-term use process is improved; meanwhile, the side chain of the rigid benzene ring structure can endow the polymer substrate with certain hardness, so that the scratch resistance of the composite material is further improved; meanwhile, the heat resistance and the oxidation resistance of the material can be improved, so that the material is not easy to separate out and stick in the actual use process, and the application of the bio-based polysiloxane scratch-resistant auxiliary agent to the scratch composite material is facilitated. Experimental results show that when the bio-based polysiloxane scratch-resistant auxiliary agent provided by the invention is used for a scratch-resistant composite material, the visibility of surface scratches of the scratch-resistant composite material is reduced and the scratch resistance of the composite material is obviously improved through a three-dimensional super-depth-of-field microscope test; meanwhile, the depth of the wave trough of the scraping surface of the polypropylene substrate is 6306nm, and the depth of the wave trough of the scraping surface of the scraping-resistant polypropylene composite material is 3646nm, so that the obtained novel bio-based polysiloxane scraping-resistant auxiliary agent can obviously improve the scraping-resistant performance of the polymer substrate.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of an intermediate produced in example 1 of the present invention;
FIG. 2 is an FTIR profile of bio-based PMHS prepared in example 1 of the present invention;
FIG. 3 is a graph of the morphology of the polypropylene sheet prepared in comparative example 1 after scratching;
FIG. 4 is a graph of surface scratch valley depth after scratching for the polypropylene sheet prepared in comparative example 1;
FIG. 5 is a topographic map of the scratch resistant polypropylene composite prepared in example 4 after scratching;
FIG. 6 is a surface scratch resistance valley depth plot of the scratch resistance polypropylene composite prepared in example 4 after scratching;
FIG. 7 is a topographic map of the scratch resistant polypropylene composite prepared in example 5 after scratching;
FIG. 8 is a surface scratch resistance valley depth plot of the scratch resistance polypropylene composite prepared in example 5 after scratching;
FIG. 9 is a topography of the scratch resistant polypropylene composite prepared in example 6 after being scratched;
FIG. 10 is a surface scratch resistance valley depth plot of the scratch resistance polypropylene composite prepared in example 6 after scratching;
FIG. 11 is a profile of the scratch resistant polypropylene composite prepared in example 7 after being scratched;
FIG. 12 is a graph of the valley depth of the surface scratch after scratching of the scratch resistant polypropylene composite prepared in example 7.
Detailed Description
The invention provides a bio-based polysiloxane scratch-resistant auxiliary agent, which has a structure shown in a formula (I):
Figure BDA0002975913690000051
in the present invention, in the formula (I), a is 0,3,4,5,6,7 or 8; b is 0,1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765. In the present invention, the formula (I) is preferably a ═ 3,4,5,6,7 or 8, b ═ 0, x ═ 0.153 to 0.205, and n ═ 0.847 to 0.795; more preferably, a is 3, b is 0, x is (0.116), and n is (0.884).
Wherein, in formula (II), b is 1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765. In the present invention, the formula (ii) is preferably b ═ 3, x ═ 0.116, and n ═ 0.884;
in the formula (III), x and n respectively represent the composition parts of two structural units, wherein x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765.
In the invention, when the bio-based polysiloxane scratch-resistant auxiliary agent is used for preparing a scratch-resistant composite material, the main chain of the scratch-resistant auxiliary agent can migrate to the surface of the material to form a layer of lubricating film in the forming process of the scratch-resistant composite material, so that the friction coefficient of the surface of the material is reduced, and the scratch-resistant performance of the material is improved; the side chain group containing the long chain can have good compatibility with a polymer base material, and the phenomenon of separation and stickiness of the material in the long-term use process is improved; meanwhile, the side chain of the rigid benzene ring structure can endow the polymer substrate with certain hardness, so that the scratch resistance of the material is further improved; meanwhile, the heat resistance and the oxidation resistance of the material can be improved, so that the material is not easy to precipitate and stick in the actual use process, and the application of the bio-based polysiloxane scratch-resistant auxiliary agent to a polymer substrate is facilitated, and the composite material with scratch resistance is obtained.
The invention provides a preparation method of a bio-based polysiloxane scratch-resistant auxiliary agent in the technical scheme, which comprises the following steps:
(1) mixing hydrogenated cardanol, an alkaline catalyst, an organic solvent and halogenated olefin, and carrying out substitution reaction to obtain an intermediate;
(2) mixing the intermediate obtained in the step (1) with a catalyst, toluene and low hydrogen-containing polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (I);
or mixing the unhydrogenated cardanol with a catalyst, toluene and low hydrogen-containing polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant assistant with the structure of the formula (II).
The preparation method comprises the steps of mixing hydrogenated cardanol, an alkaline catalyst, an organic solvent and halogenated olefin, and carrying out substitution reaction to obtain an intermediate.
In the present invention, the hydrogenated cardanol is preferably 3-pentadecylphenol. The source of the 3-pentadecylphenol is not particularly limited in the present invention, and a commercially available product well known to those skilled in the art may be used.
According to the invention, the hydrogenated cardanol contains benzene rings and long-chain alkane structures, and can have good compatibility with a polymer substrate, and the cardanol polysiloxane prepared by the hydrogenated cardanol polysiloxane can improve the scratch resistance of the polymer substrate, so that a scratch-resistant composite material is obtained.
In the present invention, the basic catalyst preferably includes one or more of potassium hydroxide, sodium hydroxide and potassium carbonate. The source of the basic catalyst in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the basic catalyst can promote the progress of the substitution reaction.
In the present invention, the organic solvent preferably includes absolute ethanol, acetone, or N, N-dimethylformamide. The source of the organic solvent is not particularly limited in the present invention, and a commercially available product known to those skilled in the art may be used. In the present invention, when the organic solvent is the above-mentioned one, it is more advantageous to promote the substitution reaction.
In the present invention, the halogenated olefin preferably includes one or more of bromopropene, 8-bromo-1-octene, 7-bromo-1-heptene, 6-bromo-1-hexene, 5-bromo-1-pentene, 4-bromo-1-butene and chloropropene. The source of the halogenated olefin is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the purity of the halogenated olefin is preferably analytical purity and above. In the invention, when the halogenated olefin is of the above type, different types of intermediates can be obtained, and a series of cardanol polysiloxane scratch-resistant auxiliary agents can be further synthesized.
In the present invention, the ratio of the amounts of the hydrogenated cardanol, the basic catalyst and the halogenated olefin is preferably (1 to 1.1): (1-1.2): (1-1.2), more preferably (1-1.1): (1.1-1.2): (1.1-1.2). In the present invention, when the amount ratio of the hydrogenated cardanol, the basic catalyst, and the halogenated olefin is in the above range, the substitution reaction can be sufficiently performed.
In the present invention, the amount of the organic solvent is preferably 30 to 60mL, and more preferably 40 to 50mL, based on 1 to 1.1mmol of the substance of the hydrogenated cardanol. In the present invention, when the amount of the organic solvent is within the above range, the progress of the substitution reaction is more advantageously promoted.
In the present invention, the mixing of the hydrogenated cardanol, the basic catalyst, the organic solvent, and the halogenated olefin is preferably performed under stirring. In the invention, the stirring speed is preferably 250-350 rpm, and more preferably 300 rpm. In the present invention, when the stirring rate is in the above range, it is advantageous to promote uniform mixing of the hydrogenated cardanol, the basic catalyst, the organic solvent, and the halogenated olefin.
According to the invention, the cashew hydrogenation cardanol is preferably dissolved in an organic solvent to obtain a hydrogenation cardanol solution, and then an alkaline catalyst and halogenated olefin are sequentially added into the hydrogenation cardanol solution.
The operation mode of dissolving the hydrogenated cardanol in the organic solvent is not particularly limited in the invention, and a solid dissolving mode known by those skilled in the art can be adopted.
After obtaining the hydrogenated cardanol solution, the present invention preferably adds an alkaline catalyst to the hydrogenated cardanol solution to obtain a first reaction solution. In the present invention, the basic catalyst is preferably added in the form of a basic catalyst solution. In the present invention, the solvent dissolving the basic catalyst is preferably water.
In the invention, the addition mode of the alkaline catalyst solution is preferably dropwise, and the dropwise addition rate is preferably 0.2-0.5 mL/s, and more preferably 0.3-0.4 mL/s. In the invention, when the alkaline catalyst solution is added dropwise, the components can be promoted to be uniformly mixed. The device for dropwise adding the alkaline catalyst solution is not particularly limited, and the dropwise adding rate can be realized. In the present invention, the means for dropping the basic catalyst solution is preferably a syringe.
In the invention, the concentration of the alkaline catalyst solution is preferably 2-5 mol/L, and more preferably 3-4 mol/L. In the present invention, when the concentration of the basic catalyst solution is in the above range, it is more advantageous to control the reaction rate.
After the first reaction solution is obtained, the halogenated olefin is preferably added to the first reaction solution to obtain a second reaction solution in the present invention. In the invention, the halogenated olefin is preferably added dropwise, and the dropwise adding rate is preferably 0.06-0.12 mL/s, and more preferably 0.08-0.1 mL/s. In the invention, when the halogenated olefin is added dropwise, the halogenated olefin can be uniformly mixed in the reaction liquid, and the reaction rate is controlled. The device for adding the halogenated olefin dropwise is not particularly limited, and the above-mentioned addition rate can be achieved. In the present invention, the means for dropping the halogenated olefin is preferably a syringe.
After the second reaction solution is obtained, the second reaction solution is subjected to substitution reaction to obtain an intermediate.
In the invention, the temperature of the substitution reaction is preferably 78-85 ℃, and more preferably 80-85 ℃; the time of the substitution reaction is preferably 7-10 h, and more preferably 8-9 h. In the present invention, when the temperature and time of the substitution reaction are within the above ranges, the substitution reaction is more advantageously carried out.
In the present invention, the substitution reaction is preferably carried out under heating reflux in an oil bath. The operation mode of the oil bath heating reflux is not particularly limited in the present invention, and the operation mode known to those skilled in the art can be adopted. In the present invention, the oil bath heating reflux can prevent the solvent from being evaporated to dryness.
In the present invention, the substitution reaction is preferably carried out under stirring. In the invention, the stirring speed is preferably 250-350 rpm, and more preferably 300 rpm. In the present invention, when the stirring rate is in the above range, the progress of the substitution reaction can be promoted by promoting the sufficient mixing of the reagents in the second reaction solution.
After the substitution reaction is completed, the present invention preferably sequentially purifies and dries the system after the substitution reaction to obtain an intermediate.
In the present invention, the purification preferably includes removal of by-products and column chromatography, which are sequentially performed.
In the present invention, the operation of removing the by-products is preferably: and (3) separating out KBr generated in the system reaction solution after the substitution reaction by using ethyl acetate, filtering to obtain a filtrate, and performing rotary evaporation. In the invention, the temperature during rotary evaporation is preferably 45-60 ℃, and more preferably 50-55 ℃. In the present invention, the spin-evaporation time is not particularly limited, and the solvent may be removed.
The process of removing the by-products is preferably repeated until a substantial portion of the KBr is removed. In the present invention, the number of times of repeating the process of removing the by-products is preferably 2 to 4 times, and more preferably 2 to 3 times. In the invention, since column chromatography is required after the operation of removing the by-product, the number of times of repeating the process of removing the by-product is in the above range, most of KBr can be removed, and a small amount of remaining KBr in the system can be removed by the subsequent column chromatography.
In the invention, the eluent for column chromatography is preferably a mixed solution of petroleum ether and ethyl acetate; the volume ratio of the petroleum ether to the ethyl acetate in the mixed liquid is preferably (10-20): (1-1.5). More preferably (10-20): 1. In the present invention, when the eluent is of the above-mentioned kind, the intermediate can be sufficiently purified from the system from which the by-products are removed.
In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 65-75 ℃; the drying time is preferably 10-12 h; more preferably 11 to 12 hours. The drying apparatus of the present invention is not particularly limited, and any drying apparatus known to those skilled in the art may be used. In the present invention, the drying device is preferably a vacuum drying oven.
After the intermediate is obtained, the intermediate is mixed with a catalyst, toluene and low hydrogen-containing polysiloxane to carry out hydrosilylation reaction, and the bio-based polysiloxane scratch-resistant auxiliary agent is obtained.
In the present invention, the catalyst preferably includes chloroplatinic acid, a kast catalyst or an Rh catalyst. The source of the catalyst in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, when the catalyst is of the above-mentioned type, the progress of the hydrosilylation reaction can be promoted.
In the present invention, the low hydrogen polysiloxane is preferably a polymethylhydrosiloxane content of not higher than 3%, more preferably not higher than 0.56%, most preferably not higher than 0.35%, per hundred grams of low hydrogen polysiloxane. The source of the low hydrogen polysiloxane is not particularly limited in the present invention, and the above conditions can be satisfied by using a commercially available product well known to those skilled in the art. In the present invention, the source of the low hydrogen polysiloxane is preferably from gorgon silicone ltd, mountain. In the invention, when the low hydrogen-containing polysiloxane is of the above type, the obtained bio-based polysiloxane scratch-resistant assistant is more favorable for improving the scratch resistance effect of the composite material when used for preparing a scratch-resistant composite material.
In the present invention, the ratio of the amount of the intermediate to the amount of the catalyst and the low hydrogen polysiloxane is preferably (10 to 14): (4.5X 10)-7～8.0×10-7): (10-12), more preferably (10-13): (5.0X 10)-7～7.0×10-7): (11-12). In the present invention, when the ratio of the intermediate to the amount of the catalyst and the low hydrogen-containing polysiloxane is in the above range, the hydrosilylation reaction can be sufficiently performed.
The operation mode of mixing the intermediate with the catalyst, the toluene and the low hydrogen polysiloxane is not particularly limited in the present invention, and the mixing mode known to those skilled in the art can be adopted.
In the invention, the intermediate, the catalyst and the toluene are preferably mixed to obtain a mixed solution, then the mixed solution is subjected to olefin activation reaction, and then the low hydrogen-containing polysiloxane solution is added.
The operation mode of mixing the intermediate, the catalyst and the toluene is not particularly limited in the invention, and the mixing mode known to those skilled in the art can be adopted.
In the present invention, the catalyst is preferably mixed with the intermediate and toluene in the form of a catalyst solution. In the present invention, the solvent of the catalyst solution is preferably isopropyl alcohol. The concentration of the catalyst solution is preferably 0.008 to 0.012mol/L, and more preferably 0.009 to 0.01 mol/L. In the present invention, it is more advantageous to control the rate of the reaction when the concentration of the catalyst solution is within the above range.
In the invention, the temperature of the olefin activation reaction is preferably 45-55 ℃, and more preferably 50-55 ℃; the olefin activation reaction time is preferably 0.5-1 h, and more preferably 0.6-0.8 h. In the invention, when the temperature and time of the olefin activation reaction are within the above ranges, the olefin activation reaction between the olefin and the catalyst can be realized, and the subsequent hydrosilylation reaction is more facilitated.
In the present invention, the olefin activation reaction is preferably in N2Under protection. In the present invention, said N2The protection prevents the production of by-products.
In the present invention, the olefin activation reaction is preferably carried out under condensed reflux. In the present invention, the condensing reflux can prevent the solvent from being evaporated to dryness.
In the invention, the solvent of the low hydrogen-containing polysiloxane solution is preferably toluene, and the concentration of the low hydrogen-containing polysiloxane solution is preferably 0.25-0.5 mol/L, and more preferably 0.3-0.4 mol/L. In the present invention, it is more advantageous to control the reaction rate when the concentration of the low hydrogen-containing polysiloxane solution is within the above range.
In the invention, the low hydrogen-containing polysiloxane solution is preferably added dropwise, and the dropwise adding speed is preferably 1-2 mL/min, and more preferably 1.5-2 mL/min. In the invention, as hydrosilylation is an exothermic reaction, the dropping speed of the low hydrogen-containing polysiloxane solution is too high, so that a violent chemical reaction can be caused, a large amount of heat is instantaneously released to quickly raise the temperature of the system, and the solution in the reactor boils suddenly, becomes yellow and even becomes gel. In the present invention, when the dropping rate of the low hydrogen-containing polysiloxane solution is within the above range, it is more advantageous to control the reaction rate of the hydrosilylation reaction.
In the invention, the temperature of the hydrosilylation reaction is preferably 75-85 ℃, and more preferably 80-85 ℃; the time of the hydrosilylation reaction is preferably 3.5 to 4.5 hours, and more preferably 4.0 to 4.5 hours. In the invention, the hydrosilylation reaction occurs during the process of adding the low hydrogen polysiloxane solution. In the present invention, the hydrosilylation reaction can be sufficiently performed by controlling the temperature and time of the hydrosilylation reaction within the above ranges.
In the present invention, the hydrosilylation reaction is preferably carried out in N2Under protection. In the present invention, said N2The protection can prevent the occurrence of by-products.
After the hydrosilylation reaction is finished, the invention preferably removes impurities and dries the product after the hydrosilylation reaction in sequence to obtain the bio-based polysiloxane scratch-resistant auxiliary agent.
In the invention, the impurity removal is preferably evaporation, and the device adopted by the evaporation is preferably a rotary evaporator. In the invention, the evaporation temperature is preferably 80-90 ℃, and more preferably 85-90 ℃. In the present invention, the time for the evaporation is not particularly limited, and the unreacted reactant may be removed.
In the invention, the drying temperature is preferably 80-95 ℃, and more preferably 85-95 ℃. In the present invention, the drying time is not particularly limited, and the amount of the solid obtained by removing the unreacted reactant can be adjusted according to the weight of the substance to be dried.
The preparation method provided by the invention is simple to operate and easy to control, and is beneficial to obtaining the environment-friendly bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (I).
According to the invention, unhydrogenated cardanol is mixed with a catalyst, toluene and low hydrogen-containing polysiloxane, and a hydrosilylation reaction is carried out, so as to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of formula (II).
In the present invention, the unhydrogenated cardanol is preferably C15The unhydrogenated cardanol having 1 to 3 double bonds thereon is more preferably represented by formula (IV). The structural formula of formula (IV) is preferably as follows:
Figure BDA0002975913690000111
in the present invention, b in the formula (IV) is preferably 0,1,2 or 3.
In the present invention, the ratio of the amount of the unhydrogenated cardanol to the amount of the catalyst and the low hydrogen-containing polysiloxane is preferably (10 to 14): (4.5X 10)-7～8.0×10-7): (10-12), more preferably (10-13): (5.0X 10)-7～7.0×10-7): (11-12). In the present invention, when the ratio of the unhydrogenated cardanol to the amount of the catalyst and the low hydrogen-containing polysiloxane is in the above range, the hydrosilylation reaction can be sufficiently performed.
In the invention, the operation method for mixing the unhydrogenated cardanol with the catalyst, the toluene and the low hydrogen-containing polysiloxane to perform the hydrosilylation reaction to obtain the bio-based polysiloxane scratch resistant assistant with the structure shown in the formula (II) is the same as the method for mixing the intermediate obtained in the step (1) with the catalyst, the toluene and the low hydrogen-containing polysiloxane to perform the hydrosilylation reaction to obtain the bio-based polysiloxane scratch resistant assistant with the structure shown in the formula (I) in the technical scheme, and the description is omitted here.
The operation method for mixing the estragole with the catalyst, the toluene and the low hydrogen polysiloxane for the hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant aid with the structure shown in the formula (III) is the same as the method for mixing the intermediate obtained in the step (1) with the catalyst, the toluene and the low hydrogen polysiloxane for the hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant aid with the structure shown in the formula (I) in the technical scheme, and the method is not repeated here.
The invention provides a scratch-resistant composite material, which comprises a scratch-resistant auxiliary agent and a polymer substrate, wherein the scratch-resistant auxiliary agent is the bio-based polysiloxane scratch-resistant auxiliary agent in the technical scheme or the bio-based polysiloxane scratch-resistant auxiliary agent prepared by the preparation method in the technical scheme; the polymeric substrate comprises polypropylene, polycarbonate, polyamide, polymethyl methacrylate or acrylonitrile-butadiene-styrene plastic.
The sources of the polypropylene, polycarbonate, polyamide, polymethyl methacrylate and acrylonitrile-butadiene-styrene are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the scratch resistant auxiliary is preferably 0.1% to 4.0%, more preferably 0.5% to 2% by mass of the polymer substrate. In the present invention, when the amount of the scratch-resistant auxiliary is within the above range, the scratch-resistant effect of the polymer substrate can be improved, and waste caused by an excessive amount of the scratch-resistant auxiliary can be prevented.
The method for preparing the scratch-resistant composite material is not particularly limited in the invention, and the method for preparing the composite material, which is well known to those skilled in the art, can be adopted. In the present invention, the method of preparing the scratch resistant composite preferably comprises: the scratch-resistant auxiliary agent and the polymer substrate are prepared into a prepared material by an internal mixing processing technology, and then the prepared material is subjected to vacuum film pressing to obtain the scratch-resistant composite material.
In the present invention, the preparation method of the preparation material preferably comprises extrusion, banburying, injection molding or press vulcanization; more preferably, it is internal mixing.
In the invention, the parameters of the banburying processing technology are preferably as follows: the temperature first interval, the temperature second interval, the temperature third interval and the melt temperature are respectively and independently preferably 190-270 ℃, and more preferably 190-265 ℃. In the present invention, when the parameters of the banburying processing technology are in the above ranges, the scratch resistance auxiliary agent and the polymer substrate can be fully mixed.
In the invention, the process parameters of the vacuum lamination are preferably as follows: the upper die temperature is preferably 200-295 ℃, and more preferably 205-290 ℃; the lower die temperature is preferably 200-295 ℃, and more preferably 205-285 ℃; the heating time is preferably 20-30 min, and more preferably 25-30 min; the pressurizing pressure is preferably 1500-3500 kg, more preferably 2000-3000 kg; the pressurizing time is preferably 5-10 min, and more preferably 6-8 min; the mold opening temperature is preferably 25-40 ℃, and more preferably 25-30 ℃. In the invention, when the technological parameters of the vacuum lamination are in the ranges, the scratch-resistant composite material with uniform performance can be obtained more favorably.
In the present invention, the method of preparing the scratch resistant composite preferably further comprises: and (3) extruding, melting and blending. In the present invention, the process parameters of the extrusion melt blending are preferably: the rotating speed of the screw of the main machine is 180-220 r/min, and more preferably 195-205 r/min; the first temperature zone is preferably 165-175 ℃, and more preferably 170-175 ℃; the second temperature zone is preferably 170-180 ℃, and more preferably 175-180 ℃; the third temperature zone is preferably 175-185 ℃, and more preferably 180-185 ℃; the fourth temperature zone is preferably 180-190 ℃, and more preferably 185-190 ℃; the fifth temperature zone is preferably 185-195 ℃, and more preferably 190-195 ℃; the sixth temperature zone is preferably 190-200 ℃, and more preferably 195-200 ℃; the seventh temperature zone is preferably 185-195 ℃, and more preferably 190-195 ℃; the eighth temperature zone is preferably 180-190 ℃, and more preferably 185-190 ℃; the temperature range of the machine head is preferably 200-210 ℃, and more preferably 205-210 ℃. In the present invention, when the parameters of the extrusion melt blending process are within the above ranges, the scratch resistance assistant and the polymer substrate can be sufficiently mixed.
The scratch-resistant composite material provided by the invention modifies a polymer substrate by using the bio-based polysiloxane scratch-resistant auxiliary agent, and the main chain of the bio-based polysiloxane scratch-resistant auxiliary agent can migrate to the surface of the composite material to form a layer of lubricating film in the substrate forming process, so that the friction coefficient of the surface of the material is reduced, and the scratch-resistant performance of the material is improved; meanwhile, the side chain of the rigid benzene ring structure can endow the substrate with certain hardness, so that the scratch resistance of the material is further improved; meanwhile, the heat resistance and the oxidation resistance of the material can be improved, so that the material is not easy to precipitate and stick in the actual use process, and the scratch resistance of the composite material can be improved by the bio-based polysiloxane scratch resistance auxiliary agent.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding weighed 3-pentadecylphenol (10mmol, 3.0451g) serving as a cardanol derivative into 50mL of absolute ethanol solution, and stirring to dissolve the cardanol derivative to obtain a first reaction solution; adding a KOH solution with the concentration of 3mol/L into the first reaction solution at the speed of 0.2-0.5 mL/s by using an injector; gradually dropwise adding a bromopropylene (10mmol, 0.86g) solution into the first reaction solution at the speed of 0.06-0.12 mL/s by using an injector to obtain a second reaction solution; heating and refluxing the second reaction solution in an oil bath at 78 ℃ for 8 hours; precipitating KBr generated in the reacted system by using ethyl acetate, filtering to obtain a filtrate, setting the temperature to be 50 ℃ for rotary evaporation, and repeating the rotary evaporation step twice to remove the KBr; and (3) performing wet column chromatography, and eluting according to the weight ratio of petroleum ether: ethyl acetate is mixed according to the ratio of 10: 1-20: 1, and the mixture is subjected to column chromatography to obtain a purified intermediate; and (3) carrying out vacuum drying on the purified intermediate at the temperature of 60 ℃ to obtain the intermediate. (in this step, the stirring rate was controlled at 300 rpm; the ratio of the amounts of the substances of cardanol derivative (3-pentadecylphenol), the basic catalyst and bromopropene was 1: 1: 1)
The synthetic route of the intermediate is shown as the formula (V):
Figure BDA0002975913690000141
(2) mixing the intermediate (12mmol, 4.128g) obtained in the step (1), 10mL of toluene and 0.06mL of isopropanol solution of chloroplatinic acid with the concentration of 0.0096mol/L, condensing and refluxing, setting the temperature to be 50 ℃, sealing, and filling N2Protecting, and carrying out olefin activation reaction for 0.5 h; diluting 0.18% of low hydrogen polysiloxane (hereinafter referred to as PMHS) with toluene to form a solution with the concentration of 0.4mol/L, and dropwise adding the diluted low hydrogen polysiloxane solution into a system after olefin activation reaction at the speed of 1-2 mL/min by using an injector; after the dropwise addition, the oil bath temperature was set to 80 ℃, sealed and charged with N2Protecting and reacting for 4 hours; removing unreacted reactants by a rotary evaporator at the temperature of 80 ℃, and drying to obtain the cardanol-PMHS, namely the bio-based polysiloxane scratch-resistant auxiliary agent. (in this step, the ratio of the amount of the intermediate to the substances of chloroplatinic acid and low hydrogen polysiloxane was 12: 5.80X 10-7：12)
The synthetic route of the bio-based PMHS is shown as the formula (VI):
Figure BDA0002975913690000142
Figure BDA0002975913690000151
wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.0952; and n is 0.9048.
Detecting the intermediate obtained in the step (1) by using a nuclear magnetic resonance imager, and obtaining a nuclear magnetic hydrogen spectrum diagram as shown in figure 1. As can be seen from FIG. 1, the intermediate obtained in step (1) is 3-pentadecylallyloxybenzene; wherein, is residual petroleum ether solvent.
The biobased-PMHS prepared in the step (2) is detected by an infrared spectrometer, and an FTIR spectrum obtained is shown in figure 2. As can be seen from FIG. 2, the bio-based PMHS is 2160, 910cm-1Disappearance of characteristic peak at Si-H bond, 1260, 802cm-1Is Si-CH3Characteristic absorption peak of (1), 1024, 1090cm-1Is the characteristic peak of stretching vibration of Si-O-Si and C-O-C, 800cm-1Si-C stretching vibration and C-H in-plane swinging vibration are adopted, so that the completion of the hydrosilylation reaction can be seen, and the bio-based PMHS is successfully synthesized.
Example 2
The difference from example 1 is that the cardanol derivative in step (1) is unhydrogenated cardanol; the unhydrogenated cardanol is a mixture, namely a mixed phenol consisting of four phenols, namely b ═ 0,1,2 and 3. The mass ratio of the unhydrogenated cardanol, the basic catalyst and the bromopropylene is 1: 1: 1; the obtained intermediate is a mixed olefin composed of four cardanol groups, wherein the structural formula of the cardanol group mixed olefin is shown as a formula (VII):
Figure BDA0002975913690000152
wherein b is 0,1,2,3 in the formula (VII).
The ratio of the intermediate in the step (2) to the amounts of the chloroplatinic acid and the low hydrogen polysiloxane is 12: 5.80X 10-7: 12. the remaining procedure was the same as in example 1.
The structural formula of the bio-based PMHS obtained in the step (2) is shown as a formula (VIII):
Figure BDA0002975913690000161
wherein, in formula (VIII), b is 0,1,2, 3.
Example 3
Mixing estragole (12mmol, 1.78g), 10mL toluene and 0.06mL isopropanol solution of chloroplatinic acid with concentration of 0.0096mol/L, condensing and refluxing, setting temperature at 50 deg.C, sealing, and charging N2Protecting, and carrying out olefin activation reaction for 0.5 h; diluting 0.18% of low hydrogen polysiloxane (hereinafter referred to as PMHS) with toluene to form a solution with the concentration of 0.4mol/L, and dropwise adding the diluted low hydrogen polysiloxane solution into a system after olefin activation reaction at the speed of 1-2 mL/min by using an injector; after the dropwise addition, the oil bath temperature was set to 80 ℃, sealed and charged with N2Protecting and reacting for 4 hours; and removing unreacted reactants by a rotary evaporator at 80 ℃, and drying to obtain the bio-based PMHS. (in this step, the ratio of the amount of the intermediate to the substances of chloroplatinic acid and low hydrogen polysiloxane was 12: 5.80X 10-7：12)
Example 4
Preparation of scratch-resistant polypropylene composite material
(1) The bio-based polysiloxane scratch-resistant auxiliary prepared in example 1 and polypropylene are uniformly mixed by an internal mixer to obtain a prepared material. Wherein the bio-based polysiloxane scratch resistant auxiliary agent accounts for 0.5 percent of the mass of the polypropylene. The processing parameters of banburying are shown in table 1:
TABLE 1 processing parameters for internal mixing in example 4
Interval(s) Temperature is one Temperature two Temperature three Melt temperature
Temperature (. degree.C.) 210 210 210 210
(2) And (3) preparing the obtained prepared material into the scratch-resistant polypropylene composite material by using a vacuum film pressing machine, wherein the process parameters of the vacuum film pressing are as follows: temperature of the upper die: 235 ℃ and the temperature of a lower die: 235 ℃ and heating time: 25min, pressure: 1500kg, pressurization time: 5min, mold opening temperature: at 30 ℃.
Example 5
The difference from example 4 is that the bio-based polysiloxane scratch resistant aid is 1% by mass of the polypropylene, and the remaining operation method is the same as that of example 3.
Example 6
The difference from example 4 is that the bio-based polysiloxane scratch resistant aid accounts for 1.5% of the mass of the polypropylene, and the rest of the operation method is the same as that of example 4.
Example 7
The difference from example 4 is that the bio-based polysiloxane scratch resistant aid accounts for 2% of the mass of the polypropylene, and the rest of the operation method is the same as that of example 4.
Comparative example 1
The polypropylene was treated by the preparation method of example 4 to obtain a polypropylene sheet.
Example 8
Scratch Performance test
And respectively carrying out scratch resistance tests on the polypropylene plate prepared in the comparative example 1 and the scratch-resistant polypropylene composite materials prepared in the examples 4-7. The scratch operation is carried out by the method of the standard PV3952 scratch resistance test for plastic interior trim parts of the German public automobile. A cross-shaped scratch tester is used, a scratch head with the Erichsen diameter of 1.0mm is selected, the scratch load is 10N, the scratch speed is 1000mm/min, the scratch distance is 2mm, the scratch length is 40mm, and 20 scratches are respectively scraped in the longitudinal direction and the transverse direction of the sample.
The polypropylene plate prepared in comparative example 1 was tested with a three-dimensional super-depth-of-field microscope, and a topography of the scraped polypropylene plate at different magnifications is shown in fig. 3. As can be seen from FIG. 3, the polypropylene plate had a distinct scratch mark after being scratched, indicating that the scratch resistance of the polypropylene plate was poor.
The polypropylene board prepared in comparative example 1 was tested with a step profiler, and the depth curve of the scratch valley on the surface of the polypropylene board is shown in fig. 4. As can be seen from FIG. 4, the scratch depth of the polypropylene plate after being scratched is 6306 nm.
The scratch-resistant polypropylene composite material prepared in example 4 was tested with a three-dimensional super-depth-of-field microscope, and the topography of the scratched polypropylene composite material at different magnifications is shown in fig. 5. As can be seen from fig. 5, the polypropylene plate had scratches after being scratched, but the scratches were significantly reduced compared to fig. 3.
The scratch-resistant polypropylene composite material prepared in example 4 was tested by a step profiler, and a graph of depth of the scratch valley of the surface of the scratch-resistant polypropylene composite material is shown in fig. 6. As can be seen from FIG. 6, the scratch depth of the polypropylene plate after being scratched is 4833 nm.
The scratch-resistant polypropylene composite material prepared in example 5 was tested with a three-dimensional super-depth-of-field microscope, and the topography of the scratched polypropylene composite material at different magnifications is shown in fig. 7. As can be seen from fig. 7, the polypropylene plate had scratches after being scratched, but the scratches were significantly reduced compared to fig. 3.
The scratch-resistant polypropylene composite material prepared in example 5 was tested by a step profiler, and a depth curve graph of the scratch valley of the surface of the scratch-resistant polypropylene composite material is shown in fig. 8. As can be seen from FIG. 8, the scratch depth of the polypropylene plate after being scratched is 4551 nm.
The scratch-resistant polypropylene composite material prepared in example 6 was tested with a three-dimensional super-depth-of-field microscope, and the topography of the scratched polypropylene composite material at different magnifications is shown in fig. 9. As can be seen from fig. 9, the polypropylene plate has scratches after being scratched, but the scratches are significantly reduced compared to fig. 3.
The scratch-resistant polypropylene composite material prepared in example 6 was tested by a step profiler, and a graph of the depth of the surface scratch valley of the scratch-resistant polypropylene composite material is shown in fig. 10. As can be seen from FIG. 10, the scratch depth of the polypropylene plate after being scratched is 3971 nm.
The scratch-resistant polypropylene composite material prepared in example 7 was tested with a three-dimensional super-depth-of-field microscope, and the topography of the scratched polypropylene composite material at different magnifications is shown in fig. 11. As can be seen from fig. 11, the polypropylene plate had scratches after being scratched, but the scratches were significantly reduced compared to fig. 3.
The scratch-resistant polypropylene composite material prepared in example 7 was tested by a step profiler, and a graph of the depth of the surface scratch valley of the scratch-resistant polypropylene composite material is shown in fig. 12. As can be seen from FIG. 12, the scratch depth of the polypropylene plate after being scratched is 3646 nm.
As can be seen from the graphs in FIGS. 3 to 12, with the addition of the bio-based polysiloxane scratch-resistant assistant, the scratch condition of the surface of the polypropylene composite material is obviously improved, and the scratch resistance and the surface roughness of the material are improved.
Example 9
Preparation of scratch-resistant polycarbonate composite material
(1) The bio-based polysiloxane scratch-resistant auxiliary prepared in example 1 and polycarbonate were uniformly mixed by an internal mixer to obtain a prepared material. Wherein the bio-based polysiloxane scratch resistant auxiliary agent accounts for 1.0 percent of the mass of the polycarbonate. The processing parameters of banburying are shown in table 2:
TABLE 2 internal mixing processing parameters of example 9
Interval(s) Temperature one Temperature two Temperature three Melt temperature
Temperature (. degree.C.) 260 260 260 260
(2) And (3) preparing the obtained prepared material into the scratch-resistant polycarbonate composite material by using a vacuum film pressing machine, wherein the process parameters of the vacuum film pressing are as follows: temperature of the upper die: 285 ℃ and lower die temperature: 285 ℃ and heating time: 25min, pressure: 1500kg, pressurization time: 5min, mold opening temperature: at 30 ℃.
Example 10
The difference from example 9 is that the bio-based polysiloxane scratch resistant aid makes up 1.5% by mass of the polycarbonate, and the remaining operation method is the same as that of example 9.
Comparative example 2
The polycarbonate was treated by the method of example 9 to obtain a polycarbonate sheet.
Example 11
Scratch Performance test
And respectively carrying out scratch resistance tests on the polycarbonate plate prepared in the comparative example 2 and the scratch resistance polycarbonate composite materials prepared in the examples 9-10. The operation of the scraping was the same as the scraping performance test in example 8. The polycarbonate sheet prepared in comparative example 2 and the scratch-resistant polycarbonate composite materials prepared in examples 9 to 10 were tested using a step curve, and the data of the scratch valley depth thereof are shown in table 3. It can be seen that the scratch depth of the polycarbonate plate material after being scratched is 5640nm, and the scratch depth of the scratch-resistant polycarbonate composite material is 4128nm, thereby proving that the scratch resistance of the polycarbonate substrate can be obviously improved by adding the bio-based polysiloxane scratch-resistant assistant.
TABLE 3 scratch resistance test results of the scratch resistant polycarbonate composites prepared in comparative example 2 and examples 9-10
Scratch depth (nm)
Comparative example 2 5640
Example 9 4936
Example 10 4128
Example 12
Preparation of scratch-resistant polyamide composite material
(1) The bio-based polysiloxane scratch-resistant auxiliary prepared in example 1 and polyamide are uniformly mixed by an internal mixer to obtain a prepared material. Wherein the bio-based polysiloxane scratch resistant auxiliary agent accounts for 1.0 percent of the mass of the polyamide. The processing parameters of banburying are shown in table 4:
TABLE 4 Process parameters for internal mixing in example 12
Interval(s) Temperature one Temperature two Temperature three Melt temperature
Temperature (. degree.C.) 265 265 265 265
(2) And (3) preparing the obtained prepared material into the scratch-resistant polyamide composite material by using a vacuum film pressing machine, wherein the process parameters of the vacuum film pressing are as follows: temperature of the upper die: 290 ℃, temperature of lower die: 290 ℃, heating time: 25min, pressurization pressure: 1500kg, pressurization time: 5min, mold opening temperature: at 30 ℃.
Example 13
The difference from example 12 is that the bio-based polysiloxane scratch resistant aid makes up 1.5% by mass of the polyamide, and the rest of the procedure is the same as in example 12.
Comparative example 3
The polyamide was treated by the production method of example 12 to obtain a polyamide sheet.
Example 14
Scratch Performance test
And respectively carrying out scratch resistance tests on the polyamide plate prepared in the comparative example 3 and the scratch-resistant polyamide composite materials prepared in the examples 12-13. The operation of the scraping was the same as the scraping performance test in example 8. The polyamide plate prepared in comparative example 3 and the scratch-resistant polyamide composite materials prepared in examples 12 to 13 were tested by using a step curve, and the data of the scratch valley depth thereof are shown in table 5. It can be seen that the scratch depth of the scratched polyamide plate is 5447nm, and the scratch depth of the scratch-resistant polyamide composite material is 4034nm, thus proving that the scratch resistance of the polyamide substrate can be obviously improved by adding the bio-based polysiloxane scratch-resistant assistant.
TABLE 5 scratch resistance test results of the scratch resistance Polyamide composites prepared in comparative example 3 and examples 12 to 13
Figure BDA0002975913690000201
Figure BDA0002975913690000211
Example 15
Preparation of scratch-resistant polymethyl methacrylate composite material
(1) The bio-based polysiloxane scratch-resistant auxiliary prepared in example 1 and polymethyl methacrylate were uniformly mixed by an internal mixer to obtain a preliminary material. Wherein the bio-based polysiloxane scratch resistant auxiliary agent accounts for 1.0 percent of the mass of the polymethyl methacrylate. The processing parameters of banburying are shown in table 6:
TABLE 6 internal mixing processing parameters of example 15
Interval(s) Temperature one Temperature two Temperature three Melt temperature
Temperature (. degree.C.) 200 200 200 200
(2) And (3) preparing the obtained prepared material into the scratch-resistant polymethyl methacrylate composite material by using a vacuum film pressing machine, wherein the process parameters of the vacuum film pressing are as follows: temperature of the upper die: 225 ℃ and the temperature of the lower die: 225 ℃ and heating time: 25min, pressure: 1500kg, pressurization time: 5min, mold opening temperature: at 30 ℃.
Example 16
The difference from example 15 is that the bio-based polysiloxane scratch resistant assistant accounts for 1.5% of the mass of the polymethyl methacrylate, and the rest of the operation method is the same as example 15.
Comparative example 4
Polymethyl methacrylate was treated by the method of example 15 to obtain a polymethyl methacrylate plate.
Example 17
Scratch Performance test
And respectively carrying out scratch resistance tests on the polymethyl methacrylate plate prepared in the comparative example 4 and the scratch-resistant polymethyl methacrylate composite materials prepared in the examples 15-16. The operation of the scraping was the same as the scraping performance test in example 7. The polymethyl methacrylate plate prepared in comparative example 4 and the scratch-resistant polymethyl methacrylate composite materials prepared in examples 15 to 16 were tested by using a step curve, and the data of the depths of the scratch valleys are shown in table 7. It can be seen that the scratch depth of the scratched polymethyl methacrylate plate is 5046nm, and the scratch depth of the scratch-resistant polymethyl methacrylate composite material is 3634nm, so that the addition of the bio-based polysiloxane scratch-resistant assistant can obviously improve the scratch resistance of the polymethyl methacrylate substrate.
TABLE 7 scratch-resistant property test results of the scratch-resistant polymethyl methacrylate composite materials prepared in comparative example 4 and examples 15 to 16
Scratch depth (nm)
Comparison ofExample 4 5046
Example 15 4443
Example 16 3634
Example 18
Preparation of scratch-resistant acrylonitrile-butadiene-styrene composite material
(1) The bio-based polysiloxane scratch resistant additive prepared in example 1 and acrylonitrile-butadiene-styrene copolymer were uniformly mixed by an internal mixer to obtain a pre-prepared material. Wherein the bio-based polysiloxane scratch-resistant assistant accounts for 1.0 percent of the mass of the acrylonitrile-butadiene-styrene copolymer. The processing parameters of banburying are shown in Table 8:
TABLE 8 Process parameters for internal mixing in example 18
Interval(s) Temperature is one Temperature two Temperature three Melt temperature
Temperature (. degree.C.) 190 190 190 190
(2) And preparing the obtained prepared material into the scratch-resistant acrylonitrile-butadiene-styrene composite material by a vacuum film pressing machine, wherein the technological parameters of the vacuum film pressing are as follows: temperature of the upper die: 220 ℃ and the temperature of the lower die: 220 ℃ and heating time: 25min, pressure: 1500kg, pressurization time: 5min, mold opening temperature: at 30 ℃.
Example 19
The difference from example 18 was that the bio-based polysiloxane scratch resistant aid accounted for 1.5% by mass of the acrylonitrile-butadiene-styrene copolymer, and the remaining operation was the same as in example 18.
Comparative example 5
Acrylonitrile-butadiene-styrene was treated by the preparation method of example 18 to obtain acrylonitrile-butadiene-styrene sheets.
Example 20
Scratch Performance test
Scratch resistance tests are respectively carried out on the acrylonitrile-butadiene-styrene plate prepared in the comparative example 5 and the scratch-resistant acrylonitrile-butadiene-styrene composite materials prepared in the examples 18-19. The operation of the scraping was the same as the scraping performance test in example 7. The acrylonitrile-butadiene-styrene plate prepared in comparative example 5 and the scratch-resistant acrylonitrile-butadiene-styrene composite materials prepared in examples 18 to 19 were tested using a step curve, and the data of the scratch valley depth thereof are shown in table 9. It can be seen that the scratch depth of the acrylonitrile-butadiene-styrene plate after being scratched is 5970nm, and the scratch depth of the scratch-resistant acrylonitrile-butadiene-styrene composite material is 3871nm, thereby proving that the scratch resistance of the acrylonitrile-butadiene-styrene substrate can be obviously improved by adding the bio-based polysiloxane scratch-resistant auxiliary agent.
TABLE 9 scratch resistance test results of scratch resistant Acrylonitrile-butadiene-styrene composite materials prepared in comparative example 5 and examples 18 to 19
Scratch depth (nm)
Comparative example 5 5970
Example 18 4639
Example 19 3871
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A bio-based polysiloxane scratch resistance aid has a structure shown in formula (I), formula (II) or formula (III):
Figure FDA0003563124760000011
wherein a is 0,3,4,5,6,7 or 8; b is 0,1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765;
wherein, in formula (II), b is 1,2 or 3; wherein x and n respectively represent the composition parts of two structural units, x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765;
in the formula (III), x and n respectively represent the composition parts of two structural units, wherein x + n is 1, and x is 0.083-0.235; n is 0.917 to 0.765.
2. A method for preparing the bio-based polysiloxane scratch resistant aid of claim 1, comprising the steps of:
(1) mixing hydrogenated cardanol, an alkaline catalyst, an organic solvent and halogenated olefin, and carrying out substitution reaction to obtain an intermediate;
(2) mixing the intermediate obtained in the step (1) with a catalyst, toluene and low hydrogen-containing polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (I);
or mixing the unhydrogenated cardanol with a catalyst, toluene and low hydrogen-containing polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (II);
or mixing the estragole with a catalyst, toluene and low hydrogen polysiloxane, and carrying out hydrosilylation reaction to obtain the bio-based polysiloxane scratch-resistant auxiliary agent with the structure of the formula (III).
3. The method of claim 2, wherein the basic catalyst in step (1) comprises one or more of potassium hydroxide, sodium hydroxide and potassium carbonate.
4. The production method according to claim 2, wherein the halogenated olefin in the step (1) comprises one or more of bromopropene, 8-bromo-1-octene, 7-bromo-1-heptene, 6-bromo-1-hexene, 5-bromo-1-pentene, 4-bromo-1-butene and chloropropene.
5. The method according to any one of claims 2 to 4, wherein the amount ratio of the cardanol derivative, the basic catalyst and the halogenated olefin in step (1) is (1 to 1.1): (1-1.2): (1-1.2).
6. The preparation method according to claim 2, wherein the temperature of the substitution reaction in the step (1) is 78-85 ℃, and the time of the substitution reaction is 7-10 h.
7. The method according to claim 2, wherein the ratio of the amount of the intermediate to the amount of the catalyst and the low hydrogen polysiloxane in the step (2) is (10 to 14): (4.5X 10)-7～8.0×10-7)：(10～12)。
8. The method according to claim 2, wherein the temperature of the hydrosilylation reaction in step (2) is 75 to 85 ℃ and the time of the hydrosilylation reaction is 3.5 to 4.5 hours.
9. A scratch-resistant composite material comprises a scratch-resistant auxiliary agent and a polymer substrate, wherein the scratch-resistant auxiliary agent is the bio-based polysiloxane scratch-resistant auxiliary agent in claim 1 or the bio-based polysiloxane scratch-resistant auxiliary agent prepared by the preparation method in any one of claims 2 to 8; the polymeric substrate comprises polypropylene, polycarbonate, polyamide, polymethyl methacrylate or acrylonitrile-butadiene-styrene plastic.
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