CN117986726A - Lignin composite nano microsphere modified PE plastic and preparation method and application thereof - Google Patents
Lignin composite nano microsphere modified PE plastic and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229920003023 plastic Polymers 0.000 title claims abstract description 70
- 239000004033 plastic Substances 0.000 title claims abstract description 70
- 239000004005 microsphere Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 34
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 claims abstract description 30
- 235000019136 lipoic acid Nutrition 0.000 claims abstract description 30
- 229960002663 thioctic acid Drugs 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
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- 230000006750 UV protection Effects 0.000 abstract description 31
- 239000000126 substance Substances 0.000 abstract description 16
- 229920001577 copolymer Polymers 0.000 abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 description 112
- 230000000052 comparative effect Effects 0.000 description 32
- -1 Polyethylene Polymers 0.000 description 17
- 229920000573 polyethylene Polymers 0.000 description 17
- 238000000465 moulding Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 229920006113 non-polar polymer Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 239000007777 multifunctional material Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
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- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses lignin composite nano microsphere modified PE plastic and a preparation method and application thereof, and relates to the field of modified plastics. According to the preparation method of the lignin composite nano microsphere modified PE plastic, lignin and nano TiO 2 are self-assembled to form lignin composite nano microspheres, POE (maleic anhydride grafted ethylene-octene copolymer) is used as a compatilizer, and lipoic acid is adopted to regulate the interfacial properties of different substances in a system, so that the compatibility of nano TiO 2, lignin and PE is improved, the aim of providing ultraviolet resistance for PE by utilizing nano TiO 2 and lignin is fulfilled, and the ultraviolet resistance of the modified PE plastic is greatly improved.
Description
Technical Field
The invention relates to the field of modified plastics, in particular to lignin composite nano microsphere modified PE plastic and a preparation method and application thereof.
Background
Polyethylene is widely used as a general plastic, and is often applied to packaging films, mulching films, pipelines and the like due to low cost, multifunctional material performance and processability, but most of polyethylene is often exposed to sunlight, and the polyethylene is easy to undergo crosslinking, chain breakage and other reactions under sunlight irradiation, so that the service life of the polyethylene is generally low, and the ultraviolet resistance of the polyethylene is poor, so that the preparation of the polyethylene composite material with ultraviolet resistance is very important.
At present, the method for modifying polyethylene to have ultraviolet resistance is often to directly mix ultraviolet shielding agents such as lignin, titanium dioxide, zinc oxide and other polar compounds. The polyethylene is a nonpolar polymer, and has poor compatibility with polar compounds, so that uneven mixing occurs in the processing process, and meanwhile, if the polar compounds are agglomerated in the polyethylene, the mechanical properties of the polyethylene are reduced, the actual use is influenced, and the ultraviolet resistance of the composite material is reduced. The polar compounds are modified and then blended with polyethylene, so that the method is a method for improving the compatibility of the polar compounds and the polyethylene, but most of modification methods are complicated, greatly improve the production cost and are not beneficial to large-scale production and use.
The prior art provides a preparation method of lignin composite polyethylene material, which comprises the steps of homogenizing lignin, modifying, mixing with polyethylene, and improving the dispersibility and compatibility of lignin in the polyethylene material, wherein the mechanical properties of the obtained composite material are not obviously improved, and the tensile strength is only 17.3 MPa at the highest although the compatibility of lignin and the polyethylene material is improved. At the same time, this prior art does not address the uv resistance of the composite.
Disclosure of Invention
In order to solve the problem that the modified PE plastic with high ultraviolet resistance and high mechanical property can not be prepared in the prior art, the invention provides a preparation method of lignin composite nano microsphere modified PE plastic, which comprises the steps of firstly enabling lignin and nano TiO 2 to self-assemble to form lignin composite nano microsphere, then taking POE (maleic anhydride grafted ethylene-octene copolymer) as a compatilizer, adopting interfacial properties of different substances in a lipoic acid regulation system, improving compatibility of the lignin composite nano microsphere and PE, and enabling the obtained PE plastic to have excellent ultraviolet resistance and mechanical property.
The invention further aims to provide a lignin composite nano microsphere modified PE plastic.
The invention further aims to provide an application of the lignin composite nano microsphere modified PE plastic.
The above object of the present invention is achieved by the following technical scheme:
A preparation method of lignin composite nano microsphere modified PE plastic comprises the following steps:
S1, reacting quaternized lignin with nano TiO 2 under the condition that the pH value of a reaction system is acidic or neutral, and obtaining lignin composite nano microspheres after the reaction is completed;
S2, uniformly mixing the lignin composite nano microsphere, POE, lipoic acid and PE obtained in the step S1 at the temperature of 100-160 ℃, and forming after uniformly mixing to obtain modified PE plastic;
The mass ratio of the lignin composite nano microsphere, POE, lipoic acid and PE in the step S2 is (6-8): 10: (5-10): (72-77).
Quaternized lignin and nano TiO 2 are substances with ultraviolet resistance (namely ultraviolet shielding capability), and the ultraviolet resistance of a PE system can be improved by the synergistic effect. However, under the condition of not compounding in advance, the quaternized lignin and the nano TiO 2 are directly added into the PE system, so that the problems of uneven dispersion and inconsistent dispersion sites are generated, and the quaternized lignin and the nano TiO 2 are difficult to play a role in synergistically improving the ultraviolet resistance.
The purpose of the step S1 in the invention is to enable TiO 2 nano particles with ultraviolet shielding capability and quaternized lignin to self-assemble to form lignin composite nano microspheres through electrostatic adsorption, and after the lignin composite nano microspheres are added into a PE system, lignin and TiO 2 in the nano microspheres cannot be mutually separated, so that the ultraviolet shielding capability of the material can be synergistically improved. In a specific embodiment of the present invention, the mass ratio of quaternized lignin to nano TiO 2 in step S1 may be 5: (1-3).
PE (polyethylene) is used as a main body of the modified PE plastic in the invention, has a simple molecular structure, belongs to a nonpolar polymer, and can improve the ultraviolet resistance after being mixed with polar lignin, but can generate the problem of poor compatibility, so that the mechanical property of the obtained lignin composite nano microsphere modified PE plastic is reduced. Similarly, the ultraviolet resistance of the polymer material can be improved by independently doping nano TiO 2 into PE, but the nano TiO 2 has high surface energy and strong polarity, has poor compatibility with PE, has low dispersion degree in a PE system, and thus the obtained PE plastic has poor ultraviolet aging resistance stability, and meanwhile, the nano TiO 2 has strong photocatalytic capability and is easy to accelerate the degradation of the PE plastic. For the above reasons, it is necessary to add a substance such as a compatibilizer to modify the quaternized lignin, the nano TiO 2, and the lignin composite nano-microsphere formed from both.
In step S2, POE (maleic anhydride grafted ethylene-octene copolymer) is used as a compatibilizer, so that the compatibility between lignin and PE can be improved. The lipoic acid can play a role in interface regulation in a PE system added with the composite nano-microsphere, the lignin composite nano-microsphere is blended with liquid molten lipoic acid at the temperature of 100-160 ℃, the lipoic acid not only improves the defect of uneven dispersion of lignin in PE (so that the dispersion degree of the lignin composite nano-microsphere in the PE system can be improved) while the lipoic acid is polymerized to form the polythiooctanoic acid, but also has strong hydrogen bonding effect between the polythiooctanoic acid and the lignin, so that a network structure with compact effect can be formed among the lignin composite nano-microsphere, the PE and the polythiooctanoic acid, and meanwhile, the polythiooctanoic acid has certain ultraviolet resistance and can synergistically improve the ultraviolet resistance of the PE together with the lignin composite nano-microsphere.
Controlling the mass ratio of the lignin composite nano microsphere, POE, lipoic acid and PE in the step S2 to be (6-8): 10: (5-10): (72-77) for ensuring the mechanical properties of the PE system while fully playing the role of the lignin composite nano-microsphere to improve the ultraviolet resistance. Too much lignin composite nano-microspheres, POE and lipoic acid can lead to the decrease of the mechanical properties of PE systems.
The lignin modified PE material prepared by the preparation method provided by the invention has stronger interface interaction, not only improves the mechanical property, but also has excellent ultraviolet resistance.
The reason that step S1 must be performed under the condition that the pH of the reaction system is acidic or neutral is that quaternized lignin is difficult to stably exist under alkaline conditions, which results in difficulty in proceeding the subsequent reaction.
The quaternized lignin described in step S1 of the present invention can be prepared by methods conventional in the art. In a specific embodiment of the present invention, the method for preparing quaternized lignin described above may include the steps of:
Weighing 0.5g of alkali lignin, dissolving in water, adjusting the pH to 9 by using sodium hydroxide, adding 0.1g of quaternizing agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and blending for 2 hours at 50 ℃ to obtain the quaternized lignin.
In a specific embodiment of the present invention, the operation of reacting quaternized lignin with nano-TiO 2 in step S1 may be: dissolving quaternized lignin in a solvent A to obtain a quaternized lignin solution, regulating pH to be acidic or neutral, dissolving nano TiO 2 in a solvent B, adding an anionic surfactant to obtain a nano TiO 2 solution, adding a nano TiO 2 solution into the quaternized lignin solution, and reacting the quaternized lignin with nano TiO 2.
It should be noted that the above reaction process is a self-assembly process, in which quaternized lignin and nano TiO 2 are self-assembled to form a composite nano microsphere by electrostatic adsorption.
More specifically, the solvent a may be water.
More specifically, the solvent B may be ethanol.
More specifically, the anionic surfactant may be sodium dodecyl benzene sulfonate.
In a specific embodiment of the present invention, the mixing process described in step S2 may be performed in an open mill, an internal mixer or a torque rheometer.
More specifically, the rotation speed of the mixing process in the step S2 is 5-15 rpm when the mixing process is performed in an open mill.
The conventional molding methods in the art are applicable to the step S2 of the present invention. In a specific embodiment of the present invention, the molding in step S2 may be hot press molding. More specifically, the hot press molding operation may be to put the molten substance obtained after mixing into a mold, hot-press the molten substance in a flat vulcanizing machine at 150 ℃ for 15min, cool and demold the molten substance, and take the molten substance out.
Preferably, step S2 also adds ZDMA.
The purpose of the step S2 is also to add ZDMA (zinc dimethacrylate) to prevent depolymerization of the finally obtained polythiooctanoic acid, thus denaturing the material and degrading the properties.
More preferably, in the step S2, the mass ratio of the ZDMA to the lipoic acid is (0.8-1.2): (5-10).
The ZDMA is used for preventing lipoic acid from depolymerizing, but too much adding amount also easily causes the mechanical property of lignin composite nano microsphere modified PE plastic to be reduced.
In a specific embodiment of the present invention, the mass ratio of the components in step S2 after defining the mass ratio of ZDMA to lipoic acid is ZDMA: lignin composite nano microsphere: POE: lipoic acid: pe= (0.8 to 1.2): (6-8): 10: (5-10): (72-77).
More preferably, in the step S2, the mass ratio of the ZDMA, the lignin composite nanoparticle, the POE, the lipoic acid and the PE is 1:7: 10: (6-7): (75-76).
When the proportion of the materials in the step S2 is in the range, the obtained lignin composite nano microsphere modified PE plastic has more excellent mechanical properties and ultraviolet resistance.
Preferably, the mixing time in the step S2 is 5-25 min.
Too short a time for insufficient mixing, too long a time for easy denaturation and decomposition of the material under high temperature conditions.
Preferably, the pH of the reaction system in the step S1 is 3 to 7.
The quaternized modified lignin can be stably present in the above pH environment.
Preferably, the reaction temperature in the step S1 is 40-60 ℃.
More preferably, the reaction time in the step S1 is 1-3 hours.
The reaction time is controlled to be 1-3 h, so that lignin and nano TiO 2 can be fully reacted, and the lignin can completely wrap nano TiO 2.
Preferably, the reaction in step S1 further comprises an aging step after completion.
The purpose of aging is to allow the lignin composite nanospheres, POE, lipoic acid and PE to be fully blended and precipitated more fully.
More preferably, the aging temperature in the step S1 is 30-50 ℃.
More preferably, the aging time in the step S1 is 1-2 hours.
The invention also protects the lignin composite nano microsphere modified PE plastic prepared by the preparation method.
The invention also protects application of the lignin composite nano microsphere modified PE plastic in preparing PE pipes and PE films.
Compared with the prior art, the invention has the following beneficial effects:
The lignin composite nano microsphere modified PE plastic prepared by the preparation method provided by the invention can obtain a PE system with high ultraviolet resistance and high mechanical property, the tensile strength is up to 17.5 MPa or more, the elongation at break is up to 1237.5% or more, the mechanical property is similar to that of a pure PE system, and the ultraviolet transmittance is only 1.2% at the highest, so that the ultraviolet resistance is excellent.
Drawings
FIG. 1 is a flow chart of the synthesis of modified PE plastic in example 1 of the invention.
FIG. 2 is a stress-strain diagram of PE plastics obtained in examples 1-6 and comparative examples 1, 4-6 according to the present invention.
FIG. 3 is a graph showing stress-strain curves of PE plastics obtained in example 2 and comparative examples 1 and 4 according to the present invention before and after UV irradiation.
FIG. 4 is a graph showing UV-vis absorption spectra of PE plastics obtained in examples 1-6 and comparative examples 1, 4-6 according to the present invention.
FIG. 5 is a schematic illustration of dumbbell type bars made of PE plastic obtained in examples and comparative examples of the present invention.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Examples 1 to 6
The embodiment provides a preparation method of lignin composite nano microsphere modified PE plastic with different mass ratios of substances in a series of step S2, which comprises the following steps:
S1, dissolving quaternized lignin in water to obtain a quaternized lignin solution, regulating the pH value to be 5, dissolving nano TiO 2 in ethanol, adding sodium dodecyl benzene sulfonate to obtain a nano TiO 2 solution, adding a nano TiO 2 solution into the quaternized lignin solution, and reacting the quaternized lignin with nano TiO 2, wherein the mass ratio of the quaternized lignin to the nano TiO 2 is 5:2, obtaining lignin composite nano-microspheres after the reaction is completed; wherein the mass ratio of the sodium dodecyl benzene sulfonate to the nano TiO 2 is 1:1, a step of;
S2, uniformly mixing the lignin composite nano microsphere, POE, lipoic acid, ZDMA and PE obtained in the step S1 at the temperature of 135 ℃ and then performing hot press molding to obtain modified PE plastic, wherein the uniform mixing process is performed in an open mill, the rotating speed is 10 rpm, and the uniform mixing time is 15 min;
the reaction temperature in the step S1 is 50 ℃, and the reaction time is 2 h;
the step S1 further comprises an aging step after the reaction is completed, wherein the aging temperature is 40 ℃, and the aging time is 1 h;
The molding mode in the step S2 is that the molten state substance obtained after uniform mixing is put into a mold, hot-pressed for 15min in a plate vulcanizing instrument at 150 ℃, cooled, demoulded and taken out;
The preparation method of the quaternized lignin in the step S1 comprises the following steps:
Weighing 0.5g of alkali lignin, dissolving in water, adjusting the pH to 9 by using sodium hydroxide, adding 0.1g of quaternizing agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and reacting for 2 hours at 50 ℃ to obtain quaternized lignin.
The mass ratio of each substance in the specific step S2 is shown in Table 1.
TABLE 1 specific mass ratio of S2 in preparation of lignin composite nanosphere modified PE Plastic in examples 1-6
Comparative example 1
A preparation method of PE plastic comprises the following steps:
Adding PE particles into an open mill for melting at the temperature of 135 ℃, wherein the rotation speed of the open mill is 10 rpm, and the melting time is 15 min; after melting, hot-press molding is carried out, thus obtaining PE plastic;
The molding mode is that the molten state substance obtained after melting is put into a mold, hot pressed for 15min in a plate vulcanizing instrument at 150 ℃, cooled, demoulded and taken out.
Comparative example 2
The preparation method of lignin composite nano microsphere modified PE plastic is different from that of example 1 in that:
Step S2 does not add lipoic acid.
Comparative example 3
The preparation method of lignin composite nano microsphere modified PE plastic is different from that of example 1 in that:
Step S2 does not add POE.
Comparative example 4
The comparative example provides a preparation method of modified PE plastic, which comprises the following steps:
Uniformly mixing quaternized lignin, nano TiO 2, POE, lipoic acid, ZDMA and PE at 135 ℃ and then performing hot press molding to obtain modified PE plastic, wherein the uniform mixing process is performed in an open mill at the rotating speed of 10 rpm and the uniform mixing time of 15 min;
the molding mode is that the molten state substance obtained after melting is put into a mold, hot pressed for 15min in a plate vulcanizing instrument at 150 ℃, cooled, demoulded and taken out;
The mass ratio of the ZDMA, the quaternized lignin, the nano TiO 2, the POE, the lipoic acid and the PE is 1:5:2:10:6:76.
Comparative examples 5 to 6
The comparative example provides a preparation method of lignin composite nano microsphere modified PE plastic with different mass ratios of substances in a series of S2, and the operation steps are carried out according to examples 1-6, and the mass ratios of the specific substances are shown in Table 2.
TABLE 2 mass ratio of specific substances in step S2 in the preparation of modified PE plastics in comparative examples 5 to 6
Comparative example 7
A preparation method of modified PE plastic comprises the following steps:
In the step S2, PE-g-MAH (maleic anhydride grafted polyethylene) is adopted to replace POE, and lipoic acid is not added;
in the step S2, the mass ratio of the ZDMA to the lignin composite nano microsphere to the PE-g-MAH to the PE is 1:7:16:76.
Performance testing
Tensile strength test: the PE plastics obtained in examples and comparative examples were prepared into dumbbell-shaped bars, and the tensile strength of the bars was measured, and the rising rate of the jig was 10mm. Min -1.
Elongation at break test: the PE plastics obtained in examples and comparative examples were prepared into dumbbell-shaped bars, and the breaking elongation of the bars was measured, and the rising rate of the jig was 10mm min -1.
Ultraviolet resistance test: preparing the PE plastics obtained in the examples and the comparative examples into rectangular bars with the thickness of 10 mu m, placing the bars in an ultraviolet-visible spectrophotometer for scanning, characterizing the ultraviolet resistance of the modified PE plastics by average ultraviolet transmittance within the range of 200-360 nm, and setting the scanning speed: 1.0 nm, scan range: 190-600 nm.
Specific performance test data are shown in the following table 3 and fig. 1 to 5:
TABLE 3 specific Performance test data for examples and comparative examples
From the data in table 3, it can be seen that, in the step S2, the mass ratio of ZDMA, lignin composite nano-microspheres, POE, lipoic acid and PE is (0.8-1.2): (6-8): 10: (5-10): in the range of (72-77), a PE system with high ultraviolet resistance and high mechanical property can be obtained, the tensile strength is up to more than 17.5 MPa, the elongation at break is up to more than 1237.5 percent, the mechanical property is similar to that of a pure PE system (comparative example 1), and the ultraviolet transmittance is only 1.2 percent at the highest, so that the lignin composite nano microsphere added in the step S1 can improve the ultraviolet resistance of PE, does not greatly influence the mechanical property of a PE matrix, and can even improve the mechanical property of PE (example 2). In examples 2 to 3, the mass ratio of the ZDMA, the lignin composite nanoparticle, the POE, the lipoic acid and the PE in the step S2 is preferably 1:7: 10: (6-7): in the range of (75-76), the mechanical properties are better, and the elongation at break and the tensile strength are higher.
The comparative example 1 is pure PE, and comparison of various performances with the comparative example 1 shows that the lignin composite nano microsphere modified PE plastic provided by the invention has greatly reduced ultraviolet transmittance and excellent ultraviolet resistance. Comparative examples 2 and 3 are lignin composite nano microsphere modified PE plastics obtained in step S2 without lipoic acid and POE, respectively, and thus the modified PE plastics obtained therefrom have insufficient ultraviolet resistance. The difference between comparative example 4 and example 2 is that in comparative example 4, quaternized lignin and nano TiO 2 are not self-assembled in advance to form lignin composite nano microsphere, but are directly added into a PE system for blending, so that lignin and TiO 2 in the obtained PE plastic are unevenly dispersed, and the ultraviolet resistance and various properties of the material cannot be synergistically improved. Comparative examples 5 to 6 are cases where the lipoic acid is too much or too little in step S2, respectively. From the results of comparative examples 5-6, it can be seen that the dosage of lipoic acid must be within a certain range to ensure the mechanical properties of PE system while fully compounding the lignin with the nano-microspheres to improve the ultraviolet resistance.
Comparative example 7 is actually a PE plastic prepared with other compatibilizing agents. From the results of this comparative example, it can be seen that PE-g-MAH has a rather limited degree of improvement in the compatibility of lignin, tiO 2 with PE systems, and thus has a limited improvement in the mechanical properties and UV resistance of the modified PE plastic.
FIG. 1 is a flow chart of the synthesis of modified PE plastic in example 1 of the invention.
FIG. 2 is a stress-strain diagram of PE plastics obtained in examples 1-6 and comparative examples 1, 4-6 according to the present invention. As can be seen from FIG. 2, the modified PE provided by the invention has mechanical properties similar to those of pure PE.
FIG. 3 is a graph showing stress-strain curves of PE plastics obtained in example 2 and comparative examples 1 and 4 according to the present invention before and after UV irradiation. As can be seen from fig. 3, compared with comparative examples 1 and 4, the modified PE plastic obtained in example 2 of the present invention has a reduced degree of mechanical property degradation after uv irradiation, and has more excellent mechanical property before uv irradiation.
FIG. 4 is a graph showing UV-vis absorption spectra of PE plastics obtained in examples 1-6 and comparative examples 1, 4-6 according to the present invention. As can be seen from FIG. 4, the modified PE plastic provided by the invention has better ultraviolet shielding capability, and ensures the ultraviolet resistance.
FIG. 5 is a schematic illustration of dumbbell type bars made of PE plastic obtained in examples and comparative examples of the present invention.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The preparation method of the lignin composite nano microsphere modified PE plastic is characterized by comprising the following steps of:
S1, reacting quaternized lignin with nano TiO 2 under the condition that the pH value of a reaction system is acidic or neutral, and obtaining lignin composite nano microspheres after the reaction is completed;
S2, uniformly mixing the lignin composite nano microsphere, POE, lipoic acid and PE obtained in the step S1 at the temperature of 100-160 ℃, and forming after uniformly mixing to obtain lignin composite nano microsphere modified PE plastic;
The mass ratio of the lignin composite nano microsphere, POE, lipoic acid and PE in the step S2 is (6-8): 10: (5-10): (72-77).
2. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 1, wherein ZDMA is further added in the step S2.
3. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 2, wherein the mass ratio of the ZDMA to the lipoic acid in the step S2 is (0.8-1.2): (5-10).
4. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 3, wherein the mass ratio of the ZDMA to the lignin composite nano microsphere to the POE to the lipoic acid to the PE in the step S2 is 1:7: 10: (6-7): (75-76).
5. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 1, wherein the mixing time in the step S2 is 5-25 min.
6. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 1, wherein the pH of the reaction system in the step S1 is 3-7.
7. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 1, wherein the reaction temperature in the step S1 is 40-60 ℃.
8. The method for preparing lignin composite nano microsphere modified PE plastic according to claim 7, wherein the reaction time in the step S1 is 1-3 h.
9. A lignin composite nanoparticle modified PE plastic prepared by the preparation method of any one of claims 1 to 8.
10. An application of the lignin composite nano microsphere modified PE plastic in preparing PE pipes and PE films according to claim 9.
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