CN120248240A - Maleic anhydride modified lignin sulfonate metal salt compatibilizer and preparation method and application thereof - Google Patents
Maleic anhydride modified lignin sulfonate metal salt compatibilizer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a maleic anhydride modified lignin sulfonic acid metal salt compatilizer, a preparation method and application thereof, wherein the maleic anhydride modified lignin sulfonic acid metal salt compatilizer is prepared by grafting and modifying lignin sulfonate with maleic anhydride under the condition of having an initiator, then zinc salt is added for continuous reaction, and after the reaction is completed, salting out and precipitating out a reaction product, and then separating, washing and drying are carried out, thus obtaining the maleic anhydride modified lignin sulfonic acid metal salt. After the prepared maleic anhydride modified lignin sulfonate metal salt compatilizer is utilized, the interfacial effect and the dispersion uniformity of the PBAT and PLA two phases are improved, the island structure of PLA/PBAT is converted into a bicontinuous structure, and the mechanical properties of the PBAT/PLA composite film product such as tensile strength, puncture strength and elongation at break are obviously improved.
Description
Technical Field
The invention belongs to the technical field of compatilizers for polyester-based composite films, relates to a maleic anhydride modified lignin sulfonic acid metal salt compatilizer, a preparation method and application thereof, and in particular relates to a method for synergistically modifying lignin sulfonate by using maleic anhydride and zinc salt, and a PBAT/PLA composite film compatibilized by using the compatilizer.
Background
In the generic term national packaging (GB 4122-83) flexible packaging is defined as packaging in which the shape of the container can be changed after filling or removal of the contents. Sheet-like plastics having a thickness of 0.25mm or less are generally referred to as films. Plastic packaging films are important guarantees for commodity transportation and storage. At present, most of plastic packaging films widely used are disposable products and cannot be degraded. Biodegradable plastics are an environmentally friendly material that can be eventually degraded into water, carbon dioxide, mineral salts, etc. by microorganisms such as algae, fungi, and bacteria that exist in nature. The biodegradable plastic package replaces the traditional disposable non-degradable plastic package, and is one of the important ways to solve the problem of white pollution.
Among the numerous biodegradable plastics, poly (butylene terephthalate)/adipate (PBAT) is a thermoplastic biodegradable highly flexible copolyester that combines the biodegradability of aliphatic backbone polymers with the mechanical properties of aromatic backbone polymers. Polylactic acid (PLA) is a biodegradable aliphatic polyester obtained by polymerization of lactic acid, has brittleness and high tensile strength, but has poor toughness, and is generally required to be blended with other plastics to improve the toughness of the polylactic acid, and the polylactic acid can be used as a good blending component for improving the strength of a tough material. It is theoretically expected that PBAT alloying with PLA maximizes the toughness of the former and the strength of the latter. However, the two molecules have large structural difference, so that the adhesive force of the blend interface is weak, and the phase separation problem affects the mechanical property of the material. In order to obtain the high-performance biodegradable packaging film, it is necessary to introduce a compatibilizer into the blend to improve the interfacial effect and dispersion uniformity of the two phases of PBAT and PLA, convert the island-in-sea structure of PLA/PBAT into a bicontinuous structure, improve the mixing effect and improve the mechanical properties of the film product.
Compatibilization modification of polymer alloys is generally accomplished by the addition of compatibilizers to improve the two-phase/multi-phase compatibility problem. The compatilizer mainly comprises reactive compatilizers such as cyclic anhydride, carboxylic acid, epoxy, isocyanate, oxazoline and the like. However, most reactive compatibilizers are complex to prepare, costly, and not biodegradable. Therefore, the development of renewable, environmentally friendly, low cost reactive compatibilizers has significant research value.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a maleic anhydride modified lignin sulfonic acid metal salt compatilizer, a preparation method and application thereof, wherein the compatilizer is prepared by utilizing maleic anhydride and zinc salt to cooperatively modify lignin sulfonate, and after the maleic anhydride modified lignin sulfonic acid metal salt compatilizer is prepared, the interfacial effect and the dispersion uniformity of PBAT and PLA two phases are improved, so that the island structure of PLA/PBAT is converted into a bicontinuous structure, and the mechanical properties of the PBAT/PLA composite film product such as tensile strength, puncture strength, elongation at break and the like are obviously improved.
In order to achieve the above object, the present invention is realized by adopting the technical scheme comprising the following technical measures.
The invention provides a preparation method of a maleic anhydride modified lignin sulfonic acid metal salt compatilizer, which mainly comprises the following steps:
and (3) grafting and modifying the lignosulfonate with maleic anhydride at 35-60 ℃ for at least 4 hours under the condition of an initiator, then adding zinc salt for continuous reaction for at least 2 hours, and separating, washing and drying a reaction product obtained by salting out and precipitation after the reaction product is reached, wherein the mass ratio of the lignosulfonate to the maleic anhydride is 1 (0.6-1.4), and the addition amount of the zinc salt is 20-100 wt% of the mass percentage of the lignosulfonate.
In this context, the lignosulfonates are a class of compounds formed by the reaction of lignin with sulfite, typically by-products of sulfite process papermaking wood pulp, and conventional commercially available raw materials including, for example, sodium lignosulfonate, calcium lignosulfonate, magnesium lignosulfonate, potassium lignosulfonate, and ammonium lignosulfonate may be selected based on low cost requirements.
In this context, the lignosulfonate is graft-modified with maleic anhydride at 35 to 60 ℃ for at least 4 hours in the presence of an initiator, wherein the initiator is selected to promote the grafting reaction of maleic anhydride with lignosulfonate, so that a person skilled in the art can select a suitable initiator according to the general knowledge of chemistry, in particular the one conventionally used in the grafting modification of maleic anhydride in the prior art.
In one technical scheme, the initiator is selected from any one of Ammonium Persulfate (APS), potassium Persulfate (PPS), sodium Persulfate (SPS) and ammonium bisulfate (AMBN), and the addition amount of the initiator is 0.5-6wt% of the mass of the maleic anhydride.
In this context, the lignosulfonate is graft-modified with maleic anhydride at 35-60 ℃ for at least 4 hours under the condition of initiator, wherein specific graft modification steps/conditions can be adapted according to the actual reaction scale and field conditions, and it should be noted that the maleic anhydride graft modification is a conventional modification manner in the prior art, and the specific graft modification steps/conditions can be directly known to those skilled in the art according to the common general knowledge in the art.
In order to better illustrate the invention and provide a technical scheme for reference, the lignosulfonate and the maleic anhydride are grafted and modified for at least 4 hours under the condition of 35-60 ℃ under the condition of an initiator, specifically, the lignosulfonate and the maleic anhydride are respectively dissolved in deionized water to respectively prepare an aqueous solution of lignosulfonate and an aqueous solution of maleic anhydride with mass concentration of 0.05-0.2 g/mL, the initiator is added into the aqueous solution of lignosulfonate, then the aqueous solution of maleic anhydride is added with stirring under the condition of 35-60 ℃ in a manner of 20-50 drops/min, and the stirring reaction is continued for at least 4 hours. It should be emphasized that this solution is used in the examples below, but this is not meant to be the only/limiting process of grafting modification of the lignosulfonate with maleic anhydride, and that the skilled person will be fully aware of the adaptations and adjustments according to the scale of the reaction and the field conditions and based on common general knowledge in the art.
In one technical scheme, the zinc salt is selected from at least one of zinc chloride, zinc sulfate, zinc acetate and zinc nitrate.
In one of the embodiments, in order to better disperse the metal salt of maleic anhydride-modified lignin sulfonate as a compatibilizer in the polyester matrix, the particle size of the metal salt of maleic anhydride-modified lignin sulfonate is preferably not higher than 100 μm. Can be obtained by grinding and sieving the dried product through a conventional sieve.
In order to better illustrate the technical effect of the invention and characterize the technical effect of the prepared maleic anhydride modified lignin sulfonic acid metal salt compatilizer, the invention also provides a preparation method for compatibilizing a PBAT/PLA composite film by using the maleic anhydride modified lignin sulfonic acid metal salt compatilizer, which mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
50-90 parts of PBAT,
10-50 Parts of polylactic acid,
0.1-5 Parts of maleic anhydride modified lignin sulfonate metal salt,
Wherein, the total weight of the PBAT and the polylactic acid is 100 parts;
(2) And (3) carrying out melt blending and film forming on the mixture obtained in the step (1) to prepare the PBAT/PLA composite film.
In this context, the polylactic acid (PLA) in step (1) is selected from conventional raw materials for polylactic acid industry, and more preferably from conventional raw materials for polylactic acid-based film products described in the prior art, and a person skilled in the art can select a suitable brand of polylactic acid according to specific needs and process requirements.
In one embodiment, the PLA in step (1) is selected from any one or more of the group consisting of vinca-survey PLA110/PLA290, nature works4032D/4060D, fengyuan FY802, marine organism REVODE, and dall L175.
The PBAT in step (1) is herein a conventional industrial raw material selection, more preferably a PBAT raw material model selection described in the prior art as suitable as packaging material, and a person skilled in the art can select a suitable PBAT brand according to specific needs and process requirements.
In one of the embodiments, in order to better disperse the metal salt of maleic anhydride-modified lignin sulfonate in the matrix, the particle size of the metal salt of maleic anhydride-modified lignin sulfonate in the step (1) is preferably not more than 100 μm. Can be obtained by grinding and sieving the dried product through a conventional sieve.
In one of the technical schemes, before the mixture in the step (2) is subjected to melt blending, the mixture can be subjected to heat drying treatment to remove moisture and ash in the mixture, and specifically, the mixture is dried for 6-12 hours at the temperature of 50-80 ℃.
In one of the technical solutions, the mixture in step (1) may further be added with additives conventionally used in polylactic acid/PBAT processing and molding to achieve further function expansion/process assistance for the product, and specific additive selection thereof may be referred to by those skilled in the art according to the prior art or the existing literature, such as processing aids/functional aids including antioxidants, lubricants, flame retardants, antioxidants, heat stabilizers, plasticizers, antibacterial agents, etc. Note that the mixture in step (1) may or may not include an auxiliary agent conventionally used in the processing and molding of polylactic acid/PBAT, and in the following preferred embodiments and specific embodiments, in order to minimize the influence factors in the comparison experiment, no auxiliary agent is added to the mixture, but this does not mean that an appropriate auxiliary agent cannot be added to the mixture. However, it should be noted that the selection and addition of the above-mentioned auxiliary agents should be based on the effect of dispersing the metal salt of maleic anhydride-modified lignin sulfonate in the matrix.
In this context, the mixture in step (2) is subjected to melt blending and film forming to prepare the PBAT/PLA composite film, wherein the melt blending is a conventional polyester-based composite material processing method using polyester as a base material, such as melt banburying, melt extrusion, and the like, and specific process steps/process parameters thereof can be directly referred to the prior art description/prior art manner of polylactic acid/PBAT during melt blending.
In one technical scheme, the mixture in the step (2) is subjected to melt blending and film forming, wherein the melt blending is performed by adopting a screw extruder, and specific process parameters are that the temperature of each zone is 130-180 ℃ and the screw rotating speed is 180-200 rpm.
In this context, the mixture in step (2) is melt blended and formed into a film to prepare the PBAT/PLA composite film, wherein the film forming is a conventional polyester-based film preparation process, such as hot-press film forming and blow-molding film forming, and specific process steps/process parameters thereof can be directly referred to the prior art description/prior art manner when polylactic acid/PBAT is prepared into a film.
In one technical scheme, the mixture in the step (2) is subjected to melt blending and film forming, wherein the film forming is formed by adopting a blow molding machine to blow mold, and the specific technological parameters are that the temperature of each region is 150-180 ℃ respectively, and the rotating speed of a screw is 30-50 rpm.
In the process of the technical scheme related subject research, the inventor searches that lignin is a reinforcing filler with great potential, the lignin is an amorphous polymer formed by connecting 3 phenylpropane units through carbon-carbon bonds and ether bonds, the molecular structure of the lignin is rich in active functional groups such as benzene rings, aliphatic hydroxyl groups, phenolic hydroxyl groups and the like, and the structure of the lignin can be modified by various means. Lignin mainly originates from byproducts of pulping and papermaking and biorefinery industries, is the second largest biomass resource with reserves inferior to cellulose in plant kingdom, is mostly used as fuel, and only 5% of industrial lignin is used for manufacturing high added value products such as additives, dispersants, surfactants and the like, thereby not only causing resource waste, but also causing secondary pollution due to combustion. However, when lignin is used as a filler in a polymer, it tends to form agglomerates in the polymer matrix due to its highly variable and complex molecular structure, which reduces the toughness and transparency of the polymer to some extent.
Based on this, the inventors have chemically modified lignin in order to solve the above-described problems. In the experimental exploration process, in order to simultaneously endow the composite film with good antibacterial property, the inventor unexpectedly discovers that the reaction product can be rapidly crystallized and separated out through weak base salting-out in the experimental process of preparing maleic anhydride and zinc chloride modified lignin sulfonate by a hydrothermal method, and surprisingly discovers that the compatibility of the PBAT/PLA composite material can be obviously improved and the mechanical property of the composite film can be improved through the cooperative modification of the maleic anhydride and the zinc chloride. In the prior art, the maleic anhydride modified lignosulfonate is usually precipitated by using an organic solvent or by using a strong acid to precipitate the reaction product, or by other more complex methods. None of the prior documents describes that its precipitation preparation is carried out by a principle based on salting out. The maleic anhydride is introduced to improve the flexibility of the molecular chain of the modified lignin and reduce the color of the lignin, and the zinc is introduced to improve the thermal stability of the modified lignin and play a role in synergistic antibacterial and antioxidant effects. And simultaneously, the mechanical property of the composite film is greatly improved by combining maleic anhydride and zinc salt to cooperatively modify lignosulfonate, and the composite film can also serve as a lubricant and a chain extender of the PBAT/PLA composite material, so that the processability of the PBAT/PLA composite material is improved.
Based on the above-mentioned invention, in one of the technical schemes, the reaction product is precipitated by salting out, specifically by adding weak base, for example, by adding any one of sodium percarbonate, sodium bicarbonate, sodium sulfite and ammonia water, and neutralizing with weak base for conventional salting out.
In one preferable technical scheme, the salting-out and precipitation reaction product is carried out by adding weak base, namely, the salting-out and precipitation reaction product is carried out by adding weak base until the pH value of the reaction solution is 1.5-7, and more preferably, the weak base is added until the pH value of the reaction solution is 2.5-3.
In one preferable embodiment, the salting-out and precipitation of the reaction product is performed by preparing a weak base into a saturated weak alkali aqueous solution and neutralizing the saturated weak alkali aqueous solution to precipitate the reaction product.
In this context, the mixing, separating, washing and drying all follow the general principles of chemical processes, and the skilled person can perform specific operations according to common general knowledge.
The invention has the following beneficial effects:
1. The invention provides a preparation method of a maleic anhydride modified lignin sulfonate metal salt compatilizer, which utilizes maleic anhydride and zinc salt to synergistically modify lignin sulfonate, increases lignin carboxyl content and introduces zinc ions into terminal carboxyl. The integral molecular structure of the maleic anhydride modified lignin sulfonate metal salt compatilizer is formed by bridging lignin and zinc ions by long aliphatic chains, and the zinc ions further bridge the long aliphatic chains and lignin to form a huge network structure, so that the molecular flexibility of a reaction product is increased, and the color of the lignin is reduced. The application of the polymer as the compatilizer can obviously improve the compatibility of polylactic acid and PBAT in the composite film and the toughness of the prepared composite film.
2. The maleic anhydride modified lignin sulfonate metal salt compatilizer provided by the invention has good antibacterial property and oxidation resistance, and zinc ions are introduced into a macromolecular chain of the maleic anhydride modified lignin through structural modification of lignin sulfonate, so that the antibacterial property and oxidation resistance of the composite film are improved by being applied as the compatilizer.
3. The preparation method has the advantages of simple preparation process, mild condition, easy operation and batch production, the adopted raw materials are environmental-friendly and digestible raw materials or low-toxicity raw materials, the raw materials are less in consumption in the reaction process, the raw materials can be recycled, and no toxic byproducts are generated, so that the preparation method belongs to an environmental-friendly method.
Drawings
FIG. 1 is a diagram showing the actual contents of sodium lignin sulfonate, sodium lignin sulfonate modified with maleic anhydride and metal lignin sulfonate modified with maleic anhydride, which are raw materials used in Synthesis example 1 and Synthesis comparative example 1 according to the present invention. Wherein SL is sodium lignin sulfonate, ML is sodium lignin sulfonate modified by maleic anhydride prepared in synthetic comparative example 1, MLZn is metal lignin sulfonate modified by maleic anhydride prepared in synthetic example 1.
FIG. 2 is a chart showing the infrared absorption spectrum of the raw material of Synthesis example 1 and the metal salt of maleic anhydride-modified lignin sulfonate. Wherein SL is sodium lignin sulfonate, MA is maleic anhydride, MLZn is maleic anhydride modified lignin sulfonate metal salt prepared in synthetic example 1.
FIG. 3 is a graph showing the comparison of the mechanical properties of the PBAT/PLA composite films prepared in comparative examples 1-3 and examples 1-3.
FIG. 4 is a graph showing comparison of puncture performance of the PBAT/PLA composite films prepared in comparative examples 1 to 3 and examples 1 to 3.
FIG. 5 is a brittle fracture surface morphology diagram of the PBAT/PLA composite film prepared in comparative examples 1-2 and example 1. Wherein, the graph (a) refers to the PBAT/PLA composite film obtained by the preparation of comparative example 1, the graph (b) refers to the PBAT/PLA composite film obtained by the preparation of comparative example 2, the graph (c) refers to the PBAT/PLA composite film obtained by the preparation of example 1, and the graphs (a 1), (b 1) and (c 1) are enlarged graphs of (a), (b) and (c), respectively.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention. While the following terms are believed to be well understood by those of ordinary skill in the art, the following definitions are set forth to aid in the description of the presently disclosed subject matter.
The invention provides a preparation method of a maleic anhydride modified lignin sulfonic acid metal salt compatilizer, which mainly comprises the following steps:
and (3) grafting and modifying the lignosulfonate with maleic anhydride at 35-60 ℃ for at least 4 hours under the condition of an initiator, then adding zinc salt for continuous reaction for at least 2 hours, and separating, washing and drying a reaction product obtained by salting out and precipitation after the reaction product is reached, wherein the mass ratio of the lignosulfonate to the maleic anhydride is 1 (0.6-1.4), and the addition amount of the zinc salt is 20-100 wt% of the mass percentage of the lignosulfonate.
In this context, the lignosulfonates are a class of compounds formed by the reaction of lignin with sulfite, typically by-products of sulfite process papermaking wood pulp, and in one embodiment, conventional commercially available raw materials including, for example, sodium lignosulfonate, calcium lignosulfonate, magnesium lignosulfonate, potassium lignosulfonate, and ammonium lignosulfonate may be selected based on low cost requirements.
In this context, the lignosulfonate is graft-modified with maleic anhydride at 35 to 60 ℃ for at least 4 hours in the presence of an initiator, wherein the initiator is selected to promote the grafting reaction of maleic anhydride with lignosulfonate, so that a person skilled in the art can select a suitable initiator according to the general knowledge of chemistry, in particular the one conventionally used in the grafting modification of maleic anhydride in the prior art.
In one embodiment, the initiator is selected from any one of Ammonium Persulfate (APS), potassium Persulfate (PPS), sodium Persulfate (SPS) and ammonium bisulfate (AMBN), and the addition amount of the initiator is 0.5-6wt% of the mass of the maleic anhydride.
In this context, the lignosulfonate is graft-modified with maleic anhydride at 35-60 ℃ for at least 4 hours under the condition of initiator, wherein specific graft modification steps/conditions can be adapted according to the actual reaction scale and field conditions, and it should be noted that the maleic anhydride graft modification is a conventional modification manner in the prior art, and the specific graft modification steps/conditions can be directly known to those skilled in the art according to the common general knowledge in the art.
In order to better illustrate the invention and provide a reference embodiment, the lignosulfonate and the maleic anhydride are grafted and modified for at least 4 hours under the condition of 35-60 ℃ under the condition of having an initiator, specifically, the lignosulfonate and the maleic anhydride are respectively dissolved in deionized water to respectively prepare an aqueous solution of lignosulfonate and an aqueous solution of maleic anhydride with mass concentration of 0.05-0.2 g/mL, the initiator is added into the aqueous solution of lignosulfonate, then the aqueous solution of maleic anhydride is added with stirring under the condition of 35-60 ℃ at a dropping rate of 20-50 drops/min, and the stirring reaction is continued for at least 4 hours. It should be emphasized that this solution is used in the examples below, but this is not meant to be the only/limiting process of grafting modification of the lignosulfonate with maleic anhydride, and that the skilled person will be fully aware of the adaptations and adjustments according to the scale of the reaction and the field conditions and based on common general knowledge in the art.
In one embodiment, the zinc salt is selected from at least one of zinc chloride, zinc sulfate, zinc acetate, and zinc nitrate.
In one of the embodiments, in order to better disperse the maleic anhydride modified metal lignosulfonate as a compatibilizer in the polyester matrix, the particle size of the maleic anhydride modified metal lignosulfonate is preferably not higher than 100 μm. Can be obtained by grinding and sieving the dried product through a conventional sieve.
In one embodiment, the mass ratio of lignosulfonate to maleic anhydride is 1 (0.6-1.4), such as 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or any range or point value therebetween.
In one embodiment, the zinc salt is added in an amount of 20-100 wt%, such as 20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、85wt％、90wt％、95wt％、100wt％ or any range or point between them, of the lignosulfonate mass percent.
In order to better illustrate the technical effect of the invention and characterize the technical effect of the prepared maleic anhydride modified lignin sulfonic acid metal salt compatilizer, the invention also provides a preparation method for compatibilizing a PBAT/PLA composite film by using the maleic anhydride modified lignin sulfonic acid metal salt compatilizer, which mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
50-90 parts of PBAT,
10-50 Parts of polylactic acid,
0.1-5 Parts of maleic anhydride modified lignin sulfonate metal salt,
Wherein, the total weight of the PBAT and the polylactic acid is 100 parts;
(2) And (3) carrying out melt blending and film forming on the mixture obtained in the step (1) to prepare the PBAT/PLA composite film.
In this context, the polylactic acid (PLA) in step (1) is selected from conventional raw materials for polylactic acid industry, and more preferably from conventional raw materials for polylactic acid-based film products described in the prior art, and a person skilled in the art can select a suitable brand of polylactic acid according to specific needs and process requirements.
In one embodiment, the PLA selection in step (1) comprises any one or more of the group consisting of vinca-survey PLA110/PLA290, nature works4032D/4060D, fengyuan FY802, marine organism REVODE110, and dall L175.
The PBAT in step (1) is herein a conventional industrial raw material selection, more preferably a PBAT raw material model selection described in the prior art as suitable as packaging material, and a person skilled in the art can select a suitable PBAT brand according to specific needs and process requirements.
In one of the embodiments, in order to better disperse the maleic anhydride modified metal lignosulfonate in the matrix, the particle size of the maleic anhydride modified metal lignosulfonate in step (1) is preferably not higher than 100 μm. Can be obtained by grinding and sieving the dried product through a conventional sieve.
In one embodiment, the metal salt of maleic anhydride modified lignin sulfonate in step (1) is 0.1 to 5 parts, for example 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part, 2.0 part, 2.5 part, 3 part, 3.5 part, 4 part, 4.5 part, 5 part, or any range or point value therebetween.
In one embodiment, the polylactic acid in the step (1) is 10 to 50 parts, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, or any range or point value therebetween.
In one embodiment, before the mixture in the step (2) is melt blended, the mixture may be optionally subjected to a heat drying treatment to remove moisture and ash in the mixture, specifically, the mixture is dried at a temperature of 50-80 ℃ for 6-12 hours.
In one embodiment, the mixture in step (1) may further comprise additives conventionally used in polylactic acid/PBAT processing to achieve further functional expansion/process assistance of the product, and specific additive selection may be referred to by those skilled in the art or in the art based on prior art references, such as antioxidants, lubricants, flame retardants, antioxidants, heat stabilizers, plasticizers, antimicrobial agents, and other processing/functional additives. Note that the mixture in step (1) may or may not include an auxiliary agent conventionally used in the processing and molding of polylactic acid/PBAT, and in the following preferred embodiments and specific embodiments, in order to minimize the influence factors in the comparison experiment, no auxiliary agent is added to the mixture, but this does not mean that an appropriate auxiliary agent cannot be added to the mixture. However, it should be noted that the selection and addition of the above-mentioned auxiliary agents should be based on the effect of dispersing the metal salt of maleic anhydride-modified lignin sulfonate in the matrix.
In this context, the mixture in step (2) is subjected to melt blending and film forming to prepare the PBAT/PLA composite film, wherein the melt blending is a conventional polyester-based composite material processing method using polyester as a base material, such as melt banburying, melt extrusion, and the like, and specific process steps/process parameters thereof can be directly referred to the prior art description/prior art manner of polylactic acid/PBAT during melt blending.
In one embodiment, the mixture in the step (2) is subjected to melt blending and film forming, wherein the melt blending is performed by adopting a screw extruder, and the specific process parameters are that the temperature of each zone is 130-180 ℃ and the screw rotating speed is 180-200 rpm.
In this context, the mixture in step (2) is melt blended and formed into a film to prepare the PBAT/PLA composite film, wherein the film forming is a conventional polyester-based film preparation process, such as hot-press film forming and blow-molding film forming, and specific process steps/process parameters thereof can be directly referred to the prior art description/prior art manner when polylactic acid/PBAT is prepared into a film.
In one embodiment, the mixture in the step (2) is subjected to melt blending and film forming, wherein the film forming is formed by adopting a blow molding machine to blow mold, and the specific process parameters are that the temperature of each region is 150-180 ℃ and the rotating speed of a screw is 30-50 rpm.
In the process of the technical scheme related subject research, the inventor searches that lignin is a reinforcing filler with great potential, the lignin is an amorphous polymer formed by connecting 3 phenylpropane units through carbon-carbon bonds and ether bonds, the molecular structure of the lignin is rich in active functional groups such as benzene rings, aliphatic hydroxyl groups, phenolic hydroxyl groups and the like, and the structure of the lignin can be modified by various means. Lignin mainly originates from byproducts of pulping and papermaking and biorefinery industries, is the second largest biomass resource with reserves inferior to cellulose in plant kingdom, is mostly used as fuel, and only 5% of industrial lignin is used for manufacturing high added value products such as additives, dispersants, surfactants and the like, thereby not only causing resource waste, but also causing secondary pollution due to combustion. However, when lignin is used as a filler in a polymer, it tends to form agglomerates in the polymer matrix due to its highly variable and complex molecular structure, which reduces the toughness and transparency of the polymer to some extent.
Based on this, the inventors have chemically modified lignin in order to solve the above-described problems. In the experimental exploration process, in order to simultaneously endow the composite film with good antibacterial property, the inventor unexpectedly discovers that the reaction product can be rapidly crystallized and separated out through weak base salting-out in the experimental process of preparing maleic anhydride and zinc chloride modified lignin sulfonate by a hydrothermal method, and surprisingly discovers that the compatibility of the PBAT/PLA composite material can be obviously improved and the mechanical property of the composite film can be improved through the cooperative modification of the maleic anhydride and the zinc chloride. In the prior art, the maleic anhydride modified lignosulfonate is usually precipitated by using an organic solvent or by using a strong acid to precipitate the reaction product, or by other more complex methods. None of the prior documents describes that its precipitation preparation is carried out by a principle based on salting out. The maleic anhydride is introduced to improve the flexibility of the molecular chain of the modified lignin and reduce the color of the lignin, and the zinc is introduced to improve the thermal stability of the modified lignin and play a role in synergistic antibacterial and antioxidant effects. And simultaneously, the mechanical property of the composite film is greatly improved by combining maleic anhydride and zinc salt to cooperatively modify lignosulfonate, and the composite film can also serve as a lubricant and a chain extender of the PBAT/PLA composite material, so that the processability of the PBAT/PLA composite material is improved.
In one embodiment, the reaction product is precipitated by salting out by adding weak base, for example, by adding any one of sodium percarbonate, sodium bicarbonate, sodium sulfite and ammonia water, and neutralizing with weak base.
In one preferred embodiment, the salting-out and precipitation of the reaction product is performed by adding weak base, and more preferably, adding weak base until the pH of the reaction solution is 1.5-7, and even more preferably, adding weak base until the pH of the reaction solution is 2.5-3.
In one preferred embodiment, the reaction product is precipitated by salting out, wherein the weak base is configured as a saturated aqueous weak base solution, and the reaction product is precipitated by neutralization by adding the saturated aqueous weak base solution.
In this context, the mixing, separating, washing and drying all follow the general principles of chemical processes, and the skilled person can perform specific operations according to common general knowledge.
The present application will be explained in further detail with reference to examples. However, those skilled in the art will appreciate that these examples are provided for illustrative purposes only and are not intended to limit the present application.
Examples
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The application should not be construed as being limited to the particular embodiments described.
1. Raw materials
Poly (butylene terephthalate)/adipate (PBAT), trade name a400, zhuhai gold hair biomaterial limited;
Polylactic acid (PLA), brand PLA110, density 1.2-1.3 g/cm 3, national academy of sciences of China's Changchun application chemistry institute;
Lignosulfonate (SL), synfat basf biotechnology limited;
Maleic Anhydride (MA), shanghai taitan technologies inc;
zinc chloride (ZnCl 2), a company of colone chemicals, inc;
Ammonium persulfate, a company of Colon chemical Co., ltd;
Anhydrous sodium carbonate (Na 2CO3), a company of colone chemicals limited, all of the city.
2. Test method
Mechanical Properties mechanical properties and puncture resistance of the composite films were tested according to standard ISO 527 and GB/T37841-2019, respectively, using an Instron 5567 Universal materials tester at a tensile rate of 50mm/min and a puncture needle drop rate of 50 mm/min.
Synthesis example 1
Respectively dissolving 6g of sodium lignin sulfonate and 6g of maleic anhydride in deionized water, respectively preparing lignin sulfonate aqueous solution and maleic anhydride aqueous solution with the mass concentration of 0.2g/mL, adding 0.24g of initiator ammonium persulfate into the lignin sulfonate aqueous solution, then adding the maleic anhydride aqueous solution in a manner of 30 drops/min with stirring at the temperature of 40 ℃, continuously stirring for reaction for 4 hours, adding 2g of zinc chloride, continuously stirring for reaction for 2 hours, salting out and precipitating a reaction product with saturated sodium carbonate aqueous solution after the time is reached, separating, washing, drying, and sieving the dried product to the particle size of not more than 100 mu m through ball milling treatment, thus obtaining the maleic anhydride modified lignin sulfonate metal salt, which is MLZn.
Synthesis of comparative example 1
Respectively dissolving 6g of sodium lignin sulfonate and 6g of maleic anhydride in deionized water, respectively preparing lignin sulfonate aqueous solution and maleic anhydride aqueous solution with the mass concentration of 0.2g/mL, adding 0.24g of initiator ammonium persulfate into the lignin sulfonate aqueous solution, then adding the maleic anhydride aqueous solution in a manner of 30 drops/min with stirring at the temperature of 40 ℃, continuing stirring for reaction for 4 hours, salting out the reaction product by using saturated sodium carbonate aqueous solution after the reaction time is reached, separating, washing, drying, and sieving the dried product to the particle size of not more than 100 mu m after ball milling treatment, thus obtaining the maleic anhydride modified sodium lignin sulfonate which is marked as ML.
Example 1
Example 1 is a method for preparing a compatibilized PBAT/PLA composite film using the metal salt of maleic anhydride modified lignin sulfonate prepared in synthesis example 1 as a compatibilizer, which mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
80 parts of PBAT, and the weight of the PBAT,
20 Parts of polylactic acid, and the components are mixed,
0.3 Parts of maleic anhydride modified lignin sulfonate metal salt;
(2) The mixture obtained in the step (1) is sequentially subjected to melt extrusion, extrusion and blow molding to prepare a PBAT/PLA composite film, which is marked as P8P2MLZn0.3;
The melting extrusion is extrusion granulation by adopting a screw extruder, wherein the specific technological parameters are that the temperature of each region is 130 ℃, 150 ℃, 170 ℃, 180 ℃ and 170 ℃ respectively, and the screw rotating speed is 200rpm;
The extrusion blow molding is carried out by adopting a blow molding machine, and the specific process parameters are that the temperatures of all the areas are 150 ℃, 170 ℃, 180 ℃, 175 ℃ and 160 ℃ respectively, and the screw rotating speed is 30rpm.
Through testing, the PBAT/PLA composite film prepared in the embodiment has the tensile strength of 25.65MPa, the elongation of 1033.61 percent and the puncture strength of 66.74N/mm.
Example 2
Example 2 is a method for preparing a compatibilized PBAT/PLA composite film using the metal salt of maleic anhydride modified lignin sulfonate prepared in synthesis example 1 as a compatibilizer, which mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
80 parts of PBAT, and the weight of the PBAT,
20 Parts of polylactic acid, and the components are mixed,
0.5 Part of maleic anhydride modified lignin sulfonate metal salt;
(2) The mixture obtained in the step (1) is sequentially subjected to melt extrusion, extrusion and blow molding to prepare a PBAT/PLA composite film, which is marked as P8P2MLZn0.5;
The melting extrusion is extrusion granulation by adopting a screw extruder, wherein the specific technological parameters are that the temperature of each region is 130 ℃, 150 ℃, 170 ℃, 180 ℃ and 170 ℃ respectively, and the screw rotating speed is 200rpm;
The extrusion blow molding is carried out by adopting a blow molding machine, and the specific process parameters are that the temperatures of all the areas are 150 ℃, 170 ℃, 180 ℃, 175 ℃ and 160 ℃ respectively, and the screw rotating speed is 30rpm.
Through testing, the PBAT/PLA composite film prepared in the embodiment has the tensile strength of 24.76MPa, the elongation of 1002.19 percent and the puncture strength of 65.85N/mm.
Example 3
Example 3 is a method for preparing a compatibilized PBAT/PLA composite film using the metal salt of maleic anhydride modified lignin sulfonate prepared in synthesis example 1 as a compatibilizer, comprising the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
80 parts of PBAT, and the weight of the PBAT,
20 Parts of polylactic acid, and the components are mixed,
1 Part of maleic anhydride modified lignin sulfonate metal salt;
(2) The mixture obtained in the step (1) is sequentially subjected to melt extrusion, extrusion and blow molding to prepare a PBAT/PLA composite film, which is marked as P8P2MLZn1;
The melting extrusion is extrusion granulation by adopting a screw extruder, wherein the specific technological parameters are that the temperature of each region is 130 ℃, 150 ℃, 170 ℃, 180 ℃ and 170 ℃ respectively, and the screw rotating speed is 200rpm;
The extrusion blow molding is carried out by adopting a blow molding machine, and the specific process parameters are that the temperatures of all the areas are 150 ℃, 170 ℃, 180 ℃, 175 ℃ and 160 ℃ respectively, and the screw rotating speed is 30rpm.
The test shows that the PBAT/PLA composite film prepared in the embodiment has the tensile strength of 20.89MPa, the elongation of 840.22% and the puncture strength of 58.46N/mm.
Comparative example 1
In comparative example 1, a metal salt of lignin sulfonate modified by maleic anhydride was not added as a comparison, and the method mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
80 parts of PBAT, and the weight of the PBAT,
20 Parts of polylactic acid;
(2) Sequentially carrying out melt extrusion, extrusion blow molding on the mixture obtained in the step (1) to prepare a PBAT/PLA composite film, namely P8P2;
The melting extrusion is extrusion granulation by adopting a screw extruder, wherein the specific technological parameters are that the temperature of each region is 130 ℃, 150 ℃, 170 ℃, 180 ℃ and 170 ℃ respectively, and the screw rotating speed is 200rpm;
The extrusion blow molding is carried out by adopting a blow molding machine, and the specific process parameters are that the temperatures of all the areas are 150 ℃, 170 ℃, 180 ℃, 175 ℃ and 160 ℃ respectively, and the screw rotating speed is 30rpm.
Through testing, the PBAT/PLA composite film prepared in this comparative example has a tensile strength of 22.52MPa, an elongation of 788.62% and a puncture strength of 60.23N/mm.
Comparative example 2
In comparative example 2, the metal salt of maleic anhydride modified lignin sulfonate was replaced with sodium lignin sulfonate as a comparison, and the method mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
80 parts of PBAT, and the weight of the PBAT,
20 Parts of polylactic acid, and the components are mixed,
0.3 Parts of sodium lignin sulfonate;
(2) Sequentially carrying out melt extrusion, extrusion blow molding on the mixture obtained in the step (1) to prepare a PBAT/PLA composite film, which is recorded as P8P2SL0.3;
The melting extrusion is extrusion granulation by adopting a screw extruder, wherein the specific technological parameters are that the temperature of each region is 130 ℃, 150 ℃, 170 ℃, 180 ℃ and 170 ℃ respectively, and the screw rotating speed is 200rpm;
The extrusion blow molding is carried out by adopting a blow molding machine, and the specific process parameters are that the temperatures of all the areas are 150 ℃, 170 ℃, 180 ℃, 175 ℃ and 160 ℃ respectively, and the screw rotating speed is 30rpm.
Through testing, the PBAT/PLA composite film prepared in this comparative example has a tensile strength of 21.57MPa, an elongation of 737.38% and a puncture strength of 58.96N/mm.
Comparative example 3
In comparative example 3, the metal salt of maleic anhydride modified lignin sulfonate was replaced with sodium lignin sulfonate as a comparison, and the method mainly comprises the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
80 parts of PBAT, and the weight of the PBAT,
20 Parts of polylactic acid, and the components are mixed,
1 Part of sodium lignin sulfonate;
(2) Sequentially carrying out melt extrusion, extrusion blow molding on the mixture obtained in the step (1) to prepare a PBAT/PLA composite film, namely P8P2SL1;
The melting extrusion is extrusion granulation by adopting a screw extruder, wherein the specific technological parameters are that the temperature of each region is 130 ℃, 150 ℃, 170 ℃, 180 ℃ and 170 ℃ respectively, and the screw rotating speed is 200rpm;
The extrusion blow molding is carried out by adopting a blow molding machine, and the specific process parameters are that the temperatures of all the areas are 150 ℃, 170 ℃, 180 ℃, 175 ℃ and 160 ℃ respectively, and the screw rotating speed is 30rpm.
Through testing, the PBAT/PLA composite film prepared in this comparative example has a tensile strength of 17.63MPa, an elongation of 578.25% and a puncture strength of 55.45N/mm.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the maleic anhydride modified lignin sulfonic acid metal salt compatilizer is characterized by mainly comprising the following steps of:
and (3) grafting and modifying the lignosulfonate with maleic anhydride at 35-60 ℃ for at least 4 hours under the condition of an initiator, then adding zinc salt for continuous reaction for at least 2 hours, and separating, washing and drying a reaction product obtained by salting out and precipitation after the reaction product is reached, wherein the mass ratio of the lignosulfonate to the maleic anhydride is 1 (0.6-1.4), and the addition amount of the zinc salt is 20-100 wt% of the mass percentage of the lignosulfonate.
2. The preparation method of the catalyst according to claim 1, wherein the initiator comprises any one of ammonium persulfate, potassium persulfate, sodium persulfate and ammonium bisulfate, and the addition amount of the initiator is 0.5-6wt% of the mass of the maleic anhydride.
3. The preparation method of the water-soluble lignin sulfonate, which is characterized in that lignosulfonate and maleic anhydride are grafted and modified for at least 4 hours under the condition of 35-60 ℃ under the condition of having an initiator, specifically, lignosulfonate and maleic anhydride are respectively dissolved in deionized water to respectively prepare an aqueous solution of lignosulfonate and an aqueous solution of maleic anhydride with mass concentration of 0.05-0.2 g/mL, the initiator is added into the aqueous solution of lignosulfonate, then the aqueous solution of maleic anhydride is added with stirring under the condition of 35-60 ℃ at a dropping rate of 20-50 drops/min, and the stirring reaction is continued for at least 4 hours.
4. The method according to claim 1, wherein the zinc salt comprises at least one of zinc chloride, zinc sulfate, zinc acetate, and zinc nitrate.
5. The method of claim 1, wherein the reaction product is precipitated by salting out by adding weak base until the pH of the reaction solution is 1.5-7.
6. The maleic anhydride modified metal lignosulfonate compatibilizer of claim 1 the maleic anhydride modified lignin sulfonate metal salt prepared by the preparation method.
7. Use of the maleic anhydride modified metal lignin sulfonate according to claim 6 as a compatibilizer.
8. A method for preparing a compatibilized PBAT/PLA composite film by using the maleic anhydride modified lignin sulfonate metal salt of claim 6, which is characterized by mainly comprising the following steps:
(1) The raw materials mainly comprising the following components in parts by weight are mixed and prepared to be used as a mixture:
50-90 parts of PBAT,
10-50 Parts of polylactic acid,
0.1-5 Parts of maleic anhydride modified lignin sulfonate metal salt,
Wherein, the total weight of the PBAT and the polylactic acid is 100 parts;
(2) And (3) carrying out melt blending and film forming on the mixture obtained in the step (1) to prepare the PBAT/PLA composite film.
9. The method of claim 8, wherein the mixture in step (2) is melt blended and film-formed, wherein the melt blending is performed by a screw extruder, and the specific process parameters are that the temperature of each zone is 130-180 ℃ and the screw rotation speed is 180-200 rpm.
10. The preparation method of the glass fiber reinforced plastic composite material, as set forth in claim 8, wherein in the step (2), the mixture is subjected to melt blending and film forming, wherein the film forming is film forming by blowing through a blowing machine, and the specific process parameters are that the temperature of each zone is 150-180 ℃ and the rotating speed of a screw is 30-50 rpm.
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