CN112759906A - Fully-biodegradable polylactic acid oil-absorbing foaming material for ocean - Google Patents
Fully-biodegradable polylactic acid oil-absorbing foaming material for ocean Download PDFInfo
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Abstract
A full-biodegradable polylactic acid oil-absorbing foaming material for oceans comprises the following substances in parts by weight: 66-93.2 parts of polylactic resin; 5-20 parts of a toughening agent; 0.5-5 parts of nucleating agent; 0.1-3 parts of a crosslinking agent; 0.2-1 part of antioxidant; 1-5 parts of foaming agent. Compared with the prior art, the polylactic acid oil absorption foaming material prepared by the invention has higher oil absorption rate, the water absorption rate is obviously lower than that of the existing product, and the characteristic of basically not absorbing water is achieved, so that the problem of absorbing both oil and water in the prior art is solved, and the problem of poor buoyancy in the use process is solved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a fully biodegradable polylactic acid oil-absorbing foaming material for oceans.
Background
With the continuous development of the world industry, the use and transportation of crude oil and various oil products have become an integral part of modern life. The oil pollution discharge is increasing day by day, and the route and the chance of oil leakage are also more and more, and oil ship tank leakage on the open sea has aroused the public's very big attention in recent years. At present, the offshore oil pollution seriously threatens the offshore ecological environment, and the oil pollution treatment of the offshore environment is inevitable, so that human beings are forced to urgently need to develop a large amount of excellent oil absorption materials.
At present, the main oil absorption materials can be divided into three major categories, namely inorganic oil absorption materials, organic synthetic oil absorption materials and organic natural oil absorption materials. Inorganic minerals include zeolites, diatomaceous earth, perlite, graphite, vermiculite, clays, and silica, which have a small amount of adsorption of non-polar organic matter. Organic synthetic materials including polypropylene foams and fiber non-woven fabrics, which are polymeric materials, are common materials for treating oil pollution due to their lipophilicity and hydrophobicity, better adsorption properties, and easy preparation and reuse compared with other types of materials, but have problems of consuming petrochemical resources and being difficult to degrade. The organic natural adsorbent includes wheat straw, corn cob, peat bog, wood fiber, bark, kenaf, etc., which have high oil absorption rate, but have poor buoyancy property, absorb water simultaneously with oil absorption, and although the hydrophobicity can be improved by modification, the cost is high.
Disclosure of Invention
The invention provides a fully biodegradable polylactic acid oil-absorbing foaming material for ocean, which is used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
a full-biodegradable polylactic acid oil-absorbing foaming material for oceans comprises the following substances in parts by weight:
the fully biodegradable polylactic acid oil absorption foaming material for the ocean is a mixture of any one or two of polylactic acid (PLLA) and polylactic acid (PDLA) mixed in any proportion.
The fully biodegradable polylactic acid oil absorption foaming material for the ocean has the melting point of 165-175 ℃.
The fully biodegradable polylactic acid oil-absorbing foaming material for the ocean is characterized in that the toughening agent is dibasic acid and dihydric alcohol series polyester with biodegradability.
The fully biodegradable polylactic acid oil absorption foaming material for the ocean is characterized in that the toughening agent is any one of polybutylene succinate (PBS), polybutylene terephthalate-adipate-butylene glycol (PBAT), polybutylene succinate-adipate-butylene glycol (PBSA) or polybutylene terephthalate-succinate-butylene glycol (PBST).
The fully biodegradable polylactic acid oil absorption foaming material for the ocean is characterized in that the nucleating agent is talcum powder (Talc) or silicon dioxide (SiO)2) And an aromatic sulfonic acid ester derivative (Lak-301).
The fully biodegradable polylactic acid oil absorption foaming material for the ocean has the mesh number of 5000-9000.
The fully biodegradable polylactic acid oil absorption foaming material for the ocean is nano-scale silicon dioxide.
The fully biodegradable polylactic acid oil absorption foaming material for the ocean is characterized in that the cross-linking agent is any one of di- (tert-butylperoxyisopropyl) benzene (BIBP), polyphenyl polymethylisocyanate (PAPI), diphenylmethane diisocyanate (MDI) or triallyl cyanurate (TAIC) or a mixture of any two or more of the di- (tert-butylperoxyisopropyl) benzene (BIBP), the polyphenyl polymethylisocyanate (PAPI), the diphenylmethane diisocyanate (MDI) or the triallyl cyanurate (TAIC) which are mixed in any proportion.
The fully biodegradable polylactic acid oil absorption foaming material for the ocean is characterized in that the antioxidant is any one or a mixture of any two or more of amine antioxidant, phenol antioxidant, phosphite antioxidant and thioester antioxidant which are mixed in any proportion.
The fully biodegradable polylactic acid oil absorption foaming material for the ocean is characterized in that the foaming agent is a carbon dioxide foaming agent.
The preparation method of the fully biodegradable polylactic acid oil absorption foaming material for the ocean comprises the following steps:
the method comprises the following steps: weighing polylactic acid, a toughening agent, a nucleating agent, a crosslinking agent and an antioxidant according to a weight ratio, and uniformly mixing in a high-speed mixer to obtain a raw material mixture;
step two: adding the mixed material obtained in the step one into a hopper of a double-screw extruder at one time, and performing extrusion granulation on the material to prepare special foaming resin;
in the second step, the length-diameter ratio of the screw of the extruder is 44-56, the rotating speed is 100-:
step three: placing the special foaming resin prepared in the step two in an oven at 80 ℃ for 4 hours, taking out, adding the special foaming resin into a hopper of extrusion foaming equipment, injecting a carbon dioxide foaming agent into the second section of the extrusion foaming equipment, and foaming by foaming extrusion equipment to obtain a polylactic acid foaming material;
in the third step, the length-diameter ratio of the extruder screw is 33-48, the rotating speed is 100-:
the invention has the advantages that: compared with the prior art, the polylactic acid oil absorption foaming material prepared by the invention has higher oil absorption rate, the water absorption rate is obviously lower than that of the existing product, and the characteristic of basically not absorbing water is achieved, so that the problem of absorbing both oil and water in the prior art is solved, and the problem of poor buoyancy in the use process is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a graph comparing the adsorption rates in various media for examples of the present invention and for comparative examples;
FIG. 2 is a schematic diagram showing the operation of the test procedure in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present 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) Weighing 76.5 parts of PLLA, 20 parts of PBAT and 1 part of nucleating agent nano SiO22 parts of cross-linking agent BIBP and 0.5 part of antioxidant, and adding the mixture into a double-screw extruder after premixing the mixture evenly in a high-speed stirrer, and performing melt extrusion, cooling and granulation on the materials to obtain the special resin for foaming.
(2) And (2) placing the special foaming resin prepared in the step (1) in an oven at 80 ℃ for 4 hours, taking out the special foaming resin, adding the special foaming resin into a hopper of extrusion foaming equipment, injecting 3 parts of carbon dioxide foaming agent into the second section of the extrusion foaming equipment, and foaming the special foaming resin by foaming extrusion equipment to obtain the foaming material.
Example 2
(1) Weighing 84.8 parts of PLLA, 5 parts of PDLA, 5 parts of PBSA, 3 parts of nucleating agent talcum powder, 1 part of crosslinking agent BIBP, 1 part of crosslinking agent TAIC and 0.2 part of antioxidant, premixing uniformly in a high-stirring machine, adding into a double-screw extruder, and performing melt extrusion, cooling and granulation on the materials to obtain the special resin for foaming.
(2) And (2) placing the special foaming resin prepared in the step (1) in an oven at 80 ℃ for 4 hours, taking out the special foaming resin, adding the special foaming resin into a hopper of extrusion foaming equipment, injecting 5 parts of carbon dioxide foaming agent into the second section of the extrusion foaming equipment, and foaming the special foaming resin by foaming extrusion equipment to obtain the foaming material.
Example 3
(1) Weighing 80.7 parts of PLLA, 15 parts of PBS, 2 parts of nucleating agent Lak-301, 2 parts of cross-linking agent PAPI and 1.0 part of antioxidant, premixing uniformly in a high-stirring machine, adding into a double-screw extruder, and performing melt extrusion, cooling and granulation on the materials to obtain the special resin for foaming.
(2) And (2) placing the special foaming resin prepared in the step (1) in an oven at 80 ℃ for 4 hours, taking out the special foaming resin, then adding the special foaming resin into a hopper of extrusion foaming equipment, simultaneously injecting 5 parts of carbon dioxide foaming agent into the second section of the extrusion foaming equipment, and foaming the special foaming resin by foaming extrusion equipment to obtain the foaming material.
Example 4
(1) Weighing 75.5 parts of PLLA, 10 parts of PDLA, 10 parts of PBST, 2 parts of nucleating agent Talc, 2 parts of cross-linking agent PAPI and 0.5 part of antioxidant, premixing uniformly in a high-stirring machine, adding into a double-screw extruder, and performing melt extrusion, cooling and granulation on the materials to obtain the special foaming resin.
(2) And (2) placing the special foaming resin prepared in the step (1) in an oven at 80 ℃ for 4 hours, taking out the special foaming resin, adding the special foaming resin into a hopper of extrusion foaming equipment, injecting 2 parts of carbon dioxide foaming agent into the second section of the extrusion foaming equipment, and foaming the special foaming resin by foaming extrusion equipment to obtain the foaming material.
Comparative example 1
(1) Weighing 95.9 parts of PLLA, 2 parts of nucleating agent Talc, 2 parts of cross-linking agent PAPI and 0.1 part of antioxidant, premixing uniformly in a high-stirring machine, adding into a double-screw extruder, and performing melt extrusion, cooling and granulation on the materials to obtain the special resin for foaming.
(2) And (2) placing the special foaming resin prepared in the step (1) in an oven at 80 ℃ for 4 hours, taking out the special foaming resin, adding the special foaming resin into a hopper of extrusion foaming equipment, injecting 5 parts of carbon dioxide foaming agent into the second section of the extrusion foaming equipment, and foaming the special foaming resin by foaming extrusion equipment to obtain the foaming material.
The foamed materials obtained in the above examples and comparative examples were subjected to an oil (water) absorption ratio test, the specific test method being as follows:
putting a certain amount of foaming material into oil (water), taking out after 1min, standing for 30s, respectively weighing the mass of the material before and after oil (water) absorption, taking the average value of 5 experiments as the final result, wherein the calculation formula of the oil (water) absorption multiplying power (Q) is as follows:
in the formula m0And m1Respectively the mass of the foaming material before oil (water) absorption.
The oil (water) absorption rate of the foamed materials prepared by the invention is shown in figure 1, all the bar charts are sequentially example 1, example 2, example 3 and example 4 from left to right and a comparison example, the invention is subjected to adsorption rate tests of three media of diesel oil, soybean oil and water, and as can be seen from the bar chart in figure 1, compared with the comparison example, the foamed materials prepared by the examples 1-4 of the invention have higher oil absorption rate for both diesel oil and soybean oil, and the water absorption rate is obviously lower than that of the comparison example. Therefore, the polylactic acid foaming material provided by the invention is not only beneficial to water body purification and oil-water separation, but also can be completely biodegraded after being used, and has great value in the application of offshore oil leakage.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A full-biodegradable polylactic acid oil-absorbing foaming material for oceans is characterized in that: the composition comprises the following substances in parts by weight:
2. the fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 1, which is characterized in that: the polylactic acid is a mixture of one or two of poly-L-lactic acid (PLLA) or poly-D-lactic acid (PDLA) mixed in any proportion.
3. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 2, which is characterized in that: the melting point of the poly-L-lactic acid is 165-175 ℃.
4. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 1, which is characterized in that: the toughening agent is binary acid dihydric alcohol series polyester with biodegradability.
5. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 4, which is characterized in that: the toughening agent is any one of polybutylene succinate (PBS), poly (terephthalic acid-adipic acid-butylene glycol ester) (PBAT), poly (succinic acid-adipic acid-butylene glycol ester) (PBSA) or poly (terephthalic acid-succinic acid-butylene glycol ester) (PBST).
6. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 1, which is characterized in that: the nucleating agent is talcum powder (Talc) and silicon dioxide (SiO)2) And an aromatic sulfonic acid ester derivative (Lak-301).
7. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 6, wherein:
the mesh number of the talcum powder is 5000-9000;
the silicon dioxide is in a nanometer level.
8. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 1, which is characterized in that: the cross-linking agent is any one or a mixture of any two or more of di- (tert-butyl peroxy isopropyl) benzene (BIBP), polyphenyl polymethylpolyisocyanate (PAPI), diphenylmethane diisocyanate (MDI) or triallyl cyanurate (TAIC) mixed in any proportion.
9. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 1, which is characterized in that: the antioxidant is any one or a mixture of more than two of amine antioxidant, phenol antioxidant, phosphite antioxidant and thioester antioxidant in any proportion.
10. The fully biodegradable polylactic acid oil absorption foaming material for the ocean according to the claim 1, which is characterized in that: the foaming agent is a carbon dioxide foaming agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116178920A (en) * | 2022-12-22 | 2023-05-30 | 银禧工程塑料（东莞）有限公司 | Light polylactic acid material and preparation method thereof |
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| CN109294187A (en) * | 2018-09-12 | 2019-02-01 | 合肥华聚微科新材料有限责任公司 | A kind of full biology base polylactic acid foam material and preparation method thereof |
| CN110922729A (en) * | 2019-12-12 | 2020-03-27 | 安徽丰原乳酸聚酯材料有限公司 | Heat-resistant polylactic acid material and preparation method thereof |
| CN111808407A (en) * | 2020-08-03 | 2020-10-23 | 山东大学 | Oil-absorbing foam and preparation method and application thereof |
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