CN114369267B - Ternary composite film material and preparation method and application thereof - Google Patents
Ternary composite film material and preparation method and application thereof Download PDFInfo
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- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention relates to a ternary composite film material and a preparation method and application thereof. The preparation method of the ternary composite film material comprises the following steps: 1-1) drying PBAT and montmorillonite and then mixing together to obtain a first master batch; 1-2) purifying, drying and ball-milling the lignin, and mixing the lignin and the first master batch together to obtain a second master batch; 1-3) carrying out hot press molding on the second master batch to obtain the ternary composite film material. The invention aims to solve the technical problem of how to provide a ternary composite film material taking a completely biodegradable polyester material as a main body, so that when 60 percent of filling material is introduced into the polyester material, the ternary composite film material still can keep better mechanical property, has excellent gas barrier property, is economic in cost and good in comprehensive performance, and is more suitable for practical use.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to a ternary composite film material and a preparation method and application thereof.
Background
In recent years, the problem of "white contamination" caused by improper disposal of plastic products (particularly films and bag products) after disposal has become a global concern. Meanwhile, various countries and regions in the world have a series of plastic forbidden policies, and the development and application of the biodegradable material are powerfully promoted. Recently, China further strengthens the restriction of plastics supervision and the treatment of plastic pollution, and develops and popularizes plastic products and substitute products with standard popularization performance, environmental protection, economy and applicability by taking recycling, easy recovery and degradability as a guide. The search for a biodegradable plastic product is becoming more urgent, wherein the economy and functionality of degradable plastics are the current research hotspots.
The poly terephthalic acid/butylene adipate (PBAT) is a completely biodegradable polyester material, mainly prepared from Adipic Acid (AA), terephthalic acid (PTA) and Butanediol (BDO) monomers by an ester exchange method, and has a molecular structure containing both a flexible aliphatic chain segment and an aromatic chain segment, so that the PBAT not only has good flexibility, but also ensures the thermal stability and mechanical property of the polymer, and is beneficial to processing the PBAT into soft plastic products such as packaging bags, plastic bags, mulching films and the like. However, PBAT has a high market price, limiting its development and spread.
It has also been studied to add a portion of filler to the PBAT to reduce its cost, but when the filler contained in the PBAT reaches 40%, its mechanical properties are drastically reduced, even to the extent that it is difficult to apply it as a thin film material.
In addition, the PBAT has high water vapor transmission rate, and cannot play a role in water retention when being used as an agricultural mulching film, so that the development and popularization of the PBAT are limited.
Disclosure of Invention
The invention mainly aims to provide a ternary composite film material and a preparation method and application thereof, and aims to solve the technical problem of how to provide a ternary composite film material taking a completely biodegradable polyester material as a main body, so that the ternary composite film material can still keep good mechanical property when 60% of fillers are introduced into the polyester material, has excellent gas barrier property, is economic in cost and good in comprehensive performance, and is more suitable for practical use.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The preparation method of the ternary composite film material provided by the invention comprises the following steps:
1-1) drying PBAT and montmorillonite and then mixing together to obtain a first master batch;
1-2) purifying, drying and ball-milling the lignin, and mixing the lignin and the first master batch together to obtain a second master batch;
1-3) carrying out hot press molding on the second master batch to obtain the ternary composite film material.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the method for preparing, wherein the lignin purification comprises the steps of:
2-1) dissolving lignin in an organic solvent, and carrying out a first reaction under the condition of stirring;
2-2) filtering the reaction product, taking the filtrate, performing rotary evaporation to recover the organic solvent, wherein the rest substance in the filtrate is the purified lignin.
Preferably, the production method is one in which the lignin is at least one selected from alkali lignin, prehydrolysis liquid lignin and kraft lignin; the organic solvent is selected from at least one of methanol, ethanol and ethyl acetate.
Preferably, in the preparation method, the montmorillonite is modified montmorillonite, and the modification steps are as follows: dispersing montmorillonite in distilled water, and adding long-chain alkyl quaternary ammonium salt to perform a second reaction; after the reaction is finished, washing with distilled water to remove unreacted reagents, filtering, drying and ball-milling; or hydrolyzing the silane coupling agent, pouring the hydrolysate into the montmorillonite, uniformly stirring, drying and ball-milling.
Preferably, the preparation method is that the long-chain alkyl quaternary ammonium salt is at least one selected from the group consisting of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide.
Preferably, in the above preparation method, the silane coupling agent is at least one selected from the group consisting of γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The ternary composite film material provided by the invention comprises the following components in percentage by mass: 40-50% of PBAT, 25-30% of montmorillonite and 25-30% of lignin, wherein the lignin is lignin purified by an organic solvent.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the ternary composite film material has a water vapor transmission coefficient Pv≤1.4×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤1.0×10-14 cm3·cm/(cm2s.Pa), a tensile strength of not less than 13MPa, and an elongation at break of not less than 200%.
Preferably, the ternary composite film material is prepared according to the preparation method.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides an application of the ternary composite film material in the fields of agricultural mulching films and packaging materials.
By the technical scheme, the ternary composite film material and the preparation method and application thereof provided by the invention at least have the following advantages:
the ternary composite film material provided by the invention contains only three components of PBAT, montmorillonite and lignin, and has excellent comprehensive performance under the condition of not adding any auxiliary agent; specifically, the water vapor transmission coefficient P thereofv≤1.4×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤1.0×10-14 cm3·cm/(cm2s.Pa), the tensile strength of which is more than or equal to 13MPa, the elongation at break of which is more than or equal to 200 percent, and can completely meet the mechanical property requirement and the gas barrier property requirement of the polyester material as a soft film material; moreover, the filler component which can be contained in the ternary composite film material can reach 60 percent, the cost of the polyester material is greatly reduced, and meanwhile, the defects that a biodegradable plastic bag in the prior art is easy to damage and hard to bear heavy objects can be avoided, so that the popularization and the application of the biodegradable polyester plastic are facilitated; furthermore, the ternary composite film material provided by the invention has extremely high gas barrier property, has excellent water retention property when used as an agricultural mulching film, has good mechanical property, cannot be damaged when being paved, has excellent biodegradability, and is green and environment-friendly.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Drawings
FIG. 1 is a drawing showing the morphology of a quenched section of a ternary composite thin film material in example 1 by SEM observation;
FIG. 2 is a drawing showing the morphology of a quenched section of the ternary composite thin film material in example 4 by SEM observation;
FIG. 3 is a SEM observation of the morphology of a quenched section of the ternary composite thin film material in example 7;
FIG. 4 is a drawing showing the morphology of a quenched section of the ternary composite thin film material in comparative example 5, as observed by SEM;
FIG. 5 is a drawing showing the morphology of a quenched section of the ternary composite thin film material in comparative example 6 by SEM observation;
FIG. 6 is a schematic view of a "brick-like wall structure" of a ternary composite film material.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to a ternary composite film material, a preparation method thereof, and specific embodiments, structures, characteristics and effects thereof according to the present invention.
The invention provides a ternary composite film material which comprises the following components in percentage by mass: 40-50% of PBAT, 25-30% of montmorillonite and 25-30% of lignin, wherein the lignin is lignin purified by an organic solvent.
In the technical scheme, 50-60% of lignin and montmorillonite filler can be doped into the PBAT, and the PBAT can still keep good mechanical property even if the proportion of the doped filler is as high as 60%; meanwhile, the ternary composite film material has excellent gas barrier property, namely after the PBAT is doped with the lignin and montmorillonite fillers by 50-60%, the material cost is greatly reduced, the defect that the PBAT has high water vapor transmission rate and is difficult to retain water is well improved on the basis of keeping the mechanical property of the PBAT, and the ternary composite film material is favorable for the vigorous popularization of the PBAT biodegradable material.
The invention also provides a preparation method of the ternary composite film material, which comprises the following steps:
1-1) drying PBAT (poly (butylene terephthalate)/adipate) and montmorillonite and then mixing together to obtain a first master batch;
1-2) purifying, drying and ball-milling the lignin, and mixing the lignin and the first master batch together to obtain a second master batch;
1-3) carrying out hot press molding on the second master batch to obtain the ternary composite film material.
In the above technical scheme, the most critical steps are "fractional mixing" and "purification of the lignin by an organic solvent".
The step-by-step mixing is to mix the montmorillonite and the PBAT together and then mix the montmorillonite and the PBAT together with the purified lignin. The design idea of step-by-step mixing comprises the steps of firstly mixing montmorillonite and PBAT to preliminarily form a mutual relation of dispersion, intercalation or coupling between the montmorillonite and the PBAT; and in the second step, lignin is added and mixed, so that the lignin is filled in gaps between the montmorillonite phase and the PBAT phase. The step-by-step mixing process can avoid the phenomenon that lignin wraps the surface of montmorillonite possibly occurring when montmorillonite and lignin are added simultaneously, avoid the action structure or group that the lignin covers the surface of montmorillonite, enable the montmorillonite to be uniformly dispersed in PBAT phase, and promote the formation of interaction between montmorillonite and PBAT. Through the step-by-step mixing process, the thermoplastic lignin polymer is used as an adhesion reinforcing agent, so that gaps between the montmorillonite phase and the PBAT phase are filled, the continuity and the compatibility between the montmorillonite phase and the PBAT phase are improved, the montmorillonite phase, the PBAT phase and the PBAT phase form a brick-like wall structure, and the ternary composite film material has excellent mechanical properties.
In the technical scheme, the PBAT is a polyester material which can be completely biodegraded, and has good biodegradability; the montmorillonite is a natural mineral resource with abundant reserves and low price, and has a unique lamellar structure. When the montmorillonite is blended with the polyester material, the mechanical property, the thermal stability and the barrier property of the composite material can be obviously improved. Montmorillonite generally exhibits hydrophilicity, has poor compatibility with polyester materials, and often shows phase separation; furthermore, gaps exist between the montmorillonite phase and the polyester material phase after mixing, so that the binary material is difficult to show satisfactory mechanical properties. The invention designs a new lignin/montmorillonite/PBAT ternary composite film material by utilizing the characteristic of the lignin, so that the lignin is filled in gaps between montmorillonite phases and polyester material phases to form a 'brick-wall-like' structure, namely, the lignin in the ternary composite film material acts like a binder in gaps between bricks in the 'brick-wall' structure, the gaps between the PBAT phases and the montmorillonite phases are filled to enable the material to be compact, and the PBAT phases and the montmorillonite phases are bonded to enable the internal form of the ternary material to be more stable.
In fact, the ternary composite film material contains a large amount of lignin, the content of the lignin can be as high as 30% at the highest, and the content level is basically equivalent to the content level of the montmorillonite filler, so the lignin in the technical scheme is used as a third reinforcing phase in the film material.
The lignin in the technical scheme is purified lignin, the lignin purified by the organic solvent has lower glass transition temperature and better melt fluidity in the processing process, and the method makes full use of the characteristics of the purified lignin, so that the lignin can better fill the gap between the montmorillonite phase and the PBAT phase and obtain better technical effect.
The lignin purification comprises the following steps: dissolving lignin in an organic solvent, and carrying out a first reaction under the stirring condition; the reaction product was then filtered. The solid matter obtained by filtration is a matter insoluble in organic solvents in lignin, and the present invention does not use this part of matter. The filtrate obtained by filtering contains organic solvent and purified lignin; performing rotary evaporation on the filtrate to recover the organic solvent, wherein the residual substance in the filtrate after the organic solvent is recovered is the purified lignin; the lignin in the technical scheme of the invention is the purified lignin.
Preferably, the lignin is selected from at least one of alkali lignin, prehydrolysis liquid lignin and kraft lignin; the organic solvent is selected from at least one of methanol, ethanol and ethyl acetate.
Preferably, in the first reaction, the ratio of the lignin to the organic solvent is 1 g: 5-15 mL, the reaction temperature is 20-30 ℃, and the stirring time is 3-12 h. The performance of the purified lignin obtained by the first reaction under the process conditions can meet the use requirements. For comparison, the process conditions for purifying lignin used in the subsequent specific examples and comparative examples are as follows: the ratio of lignin to organic solvent was 1 g: 10 mL, the reaction temperature is 25 ℃, and the stirring time is 8 h.
Preferably, the montmorillonite is modified montmorillonite, and the modification steps are as follows: dispersing montmorillonite in distilled water, and adding long-chain alkyl quaternary ammonium salt to perform a second reaction; after the reaction is finished, washing with distilled water to remove unreacted reagents, filtering, drying and ball-milling; the long-chain alkyl quaternary ammonium salt is selected from at least one of Dodecyl Trimethyl Ammonium Bromide (DTAB), hexadecyl trimethyl ammonium bromide (CTAB) and octadecyl trimethyl ammonium bromide (STAB).
Preferably, in the second reaction, the addition amount of the long-chain alkyl quaternary ammonium salt is 0.5-1.5 times of the cation exchange content of the montmorillonite, the reaction temperature is 70-90 ℃, and the stirring time is 3-5 hours. The performance of the modified montmorillonite obtained by the second reaction under the process conditions can meet the use requirements. For comparison, the process conditions of the modified montmorillonite used in the following specific examples and comparative examples are as follows: the addition amount of the long-chain alkyl quaternary ammonium salt is 1.0 time of the cation exchange content of the montmorillonite, the reaction temperature is 80 ℃, and the stirring time is 4 hours.
Preferably, the montmorillonite is modified montmorillonite, and the modification steps are as follows: hydrolyzing silane coupling agent, pouring the hydrolysate into montmorillonite, stirring uniformly, drying and ball milling. The silane coupling agent is at least one selected from gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560) and gamma-methacryloxypropyltrimethoxysilane (KH 570).
When the ternary composite film material is prepared, the equipment adopted by mixing can be a double-screw extruder, an open mill and an internal mixer; the mixing temperature is 120-150 ℃, and the mixing time is 10-30 min. The product with the performance meeting the requirement can be obtained by mixing under the process conditions. For comparison, the mixing conditions used in the following specific examples and comparative examples are as follows: the mixing temperature is 140 ℃, and the mixing time in the embodiment is 25 min; the mixing time in the comparative example was 50 min.
When the ternary composite film material is prepared, the hot-press forming temperature is 120-140 ℃, the pre-pressing pressure is 0.5-2.0 MPa, and the pressurizing pressure is 2-8 MPa. The product with the performance meeting the requirement can be obtained by carrying out hot press molding under the process conditions. For comparison, the hot press molding conditions used in the following specific examples and comparative examples are as follows: the hot-press forming temperature is 130 ℃, the pre-pressing pressure is 1.5MPa, and the pressurizing pressure is 6 MPa.
Preferably, the ternary composite film material comprises the following components in percentage by mass: 40% PBAT, 30% montmorillonite and 30% lignin, wherein the lignin is organosolv purified lignin.
The ternary composite film material prepared by the method has the water vapor transmission coefficient Pv≤1.4×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤1.0×10-14 cm3·cm/(cm2s.Pa), a tensile strength of not less than 13MPa, and an elongation at break of not less than 200%.
The invention also provides an application of the ternary composite film material in the technical fields of agricultural mulching films, packaging bags, plastic bags and the like. Agricultural plastic film, wrapping bag, plastic bag all have better mechanical properties and gas barrier property.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
Unless otherwise specified, the following materials, reagents and the like are commercially available products well known to those skilled in the art; unless otherwise specified, all methods are well known in the art. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The preparation method of the purified lignin/montmorillonite/PBAT composite film material comprises the following steps:
(1) and extracting purified lignin from the prehydrolysis liquid lignin by taking ethyl acetate as a solvent, drying the lignin by ball milling, drying the lignin with PBAT and montmorillonite, adding 50 parts of PBAT into an open mill, firstly adding 25 parts of montmorillonite for mixing, then adding 25 parts of purified lignin for mixing, and obtaining the purified lignin/montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/montmorillonite/PBAT composite master batch to obtain the purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
The morphology of the quenched surface of the ternary composite thin film material in this example observed by SEM is shown in FIG. 1. As can be seen from the attached figure 1, no obvious boundary exists between the montmorillonite phase and the PBAT phase, the quenching section is smooth and flat, and lignin completely permeates into cracks and gaps between the montmorillonite phase and the PBAT phase to form a firm brick-like wall structure.
Example 2
The preparation method of the purified lignin/montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from sulfate lignin by using ethanol as a solvent, drying the purified lignin by ball milling, drying the lignin, PBAT and montmorillonite, adding 50 parts of PBAT and 25 parts of montmorillonite into a double-screw extruder, extruding and mixing to obtain PBAT/montmorillonite composite master batches, and extruding and mixing the composite master batches and 25 parts of purified lignin to obtain purified lignin/montmorillonite/PBAT composite master batches.
(2) And carrying out hot pressing film forming on the obtained purified lignin/montmorillonite/PBAT composite master batch to obtain the purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
Example 3
The preparation method of the purified lignin/montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from alkali lignin by using methanol as a solvent, drying the lignin by ball milling, drying the lignin, PBAT and montmorillonite, adding 50 parts of PBAT into an internal mixer, firstly adding 25 parts of montmorillonite for mixing, then adding 25 parts of purified lignin, and mixing to obtain the purified lignin/montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/montmorillonite/PBAT composite master batch to obtain the purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
Example 4
The preparation method of the purified lignin/organic modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from sulfate lignin by using ethyl acetate as a solvent, performing ball milling and drying, modifying montmorillonite by using Cetyl Trimethyl Ammonium Bromide (CTAB) as a modification reagent to obtain organic modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the organic modified montmorillonite and the PBAT, adding 40 parts of PBAT into an open mill, firstly adding 30 parts of the organic modified montmorillonite for mixing, then adding 30 parts of the purified lignin, and mixing to obtain the purified lignin/organic modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/organic modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
The morphology of the quenched surface of the ternary composite thin film material in this example observed by SEM is shown in FIG. 2. As can be seen from the attached figure 2, the purified lignin shows an adhesive wire drawing effect in the modified montmorillonite and PBAT composite material, and accords with the brick-like wall structure concept provided by the invention aiming at the lignin/montmorillonite/PBAT composite material.
Example 5
The preparation method of the purified lignin/organic modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from alkali lignin by using ethanol as a solvent, performing ball milling and drying, modifying montmorillonite by using Dodecyl Trimethyl Ammonium Bromide (DTAB) as a modification reagent to obtain organic modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the organic modified montmorillonite and the PBAT, adding 40 parts of PBAT and 30 parts of organic modified montmorillonite into a double-screw extruder, extruding and mixing to obtain a PBAT/organic modified montmorillonite composite master batch, and extruding and mixing the composite master batch and 30 parts of purified lignin to obtain a purified lignin/organic modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/organic modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
Example 6
The preparation method of the purified lignin/organic modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from the prehydrolysis liquid lignin by taking methanol as a solvent, performing ball milling drying, modifying montmorillonite by taking octadecyl trimethyl ammonium bromide (STAB) as a modifying reagent to obtain organic modified montmorillonite, and performing ball milling drying; drying the purified lignin, the organic modified montmorillonite and the PBAT, adding 40 parts of PBAT into an internal mixer, firstly adding 30 parts of the organic modified montmorillonite for mixing, then adding 30 parts of the purified lignin, and mixing to obtain the purified lignin/organic modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/organic modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
Example 7
The preparation method of the purified lignin/silane modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from alkali lignin by using ethyl acetate as a solvent, performing ball milling and drying, modifying montmorillonite by using gamma-aminopropyltriethoxysilane (KH550) as a modifying reagent to obtain silane modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the silane modified montmorillonite and the PBAT, adding 40 parts of PBAT into an open mill, firstly adding 30 parts of silane modified montmorillonite for mixing, then adding 30 parts of purified lignin, and mixing to obtain the purified lignin/silane modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/silane modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
The morphology of the quenched surface of the ternary composite thin film material in this example observed by SEM is shown in FIG. 3. As can be seen from fig. 3, lignin shows an adhesive wire-drawing effect in the modified montmorillonite/PBAT composite material, and the purified lignin in this embodiment is more continuously and uniformly distributed, which conforms to the "brick-wall-like" structure concept proposed in the present invention for the lignin/montmorillonite/PBAT composite material.
Example 8
The preparation method of the purified lignin/silane modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting and purifying lignin from alkali lignin by using ethyl acetate as a solvent, performing ball milling and drying, modifying montmorillonite by using gamma-aminopropyltriethoxysilane (KH550) as a modifying reagent to obtain silane modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the silane modified montmorillonite and the PBAT, adding 40 parts of PBAT and 30 parts of silane modified montmorillonite into a double-screw extruder, extruding and mixing to obtain a PBAT/silane modified montmorillonite composite master batch, and extruding and mixing the composite master batch and 30 parts of purified lignin to obtain a purified lignin/silane modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/silane modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
Example 9
The preparation method of the purified lignin/silane modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from sulfate lignin by using methanol as a solvent, performing ball milling and drying, modifying montmorillonite by using gamma-methacryloxypropyl trimethoxy silane (KH570) as a modifying reagent to obtain silane modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the silane modified montmorillonite and the PBAT, adding 40 parts of PBAT into an internal mixer, firstly adding 30 parts of silane modified montmorillonite for mixing, then adding 30 parts of purified lignin, and mixing to obtain the purified lignin/silane modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/silane modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The performance test data of the ternary composite film material of this example are shown in table 1.
Comparative example 1
The preparation method of the lignin/montmorillonite/PBAT composite film material comprises the following steps:
(1) and drying the prehydrolysis liquid lignin, the montmorillonite and the PBAT, adding 50 parts of PBAT into an open mill, simultaneously adding 25 parts of montmorillonite and 25 parts of prehydrolysis liquid lignin, and mixing to obtain the lignin/montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained lignin/montmorillonite/PBAT composite master batch to obtain the lignin/montmorillonite/PBAT composite film material.
The data of the performance test of the ternary composite film material of the comparative example are shown in table 1.
Comparative example 2
The preparation method of the purified lignin/montmorillonite/PBAT composite film material comprises the following steps:
(1) and extracting purified lignin from the prehydrolysis liquid lignin by taking ethyl acetate as a solvent, drying the lignin by ball milling, drying the lignin with PBAT and montmorillonite, adding 50 parts of PBAT into a double-screw extruder, simultaneously adding 25 parts of montmorillonite and purified lignin, extruding and mixing to obtain the purified lignin/montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/montmorillonite/PBAT composite master batch to obtain the purified lignin/montmorillonite/PBAT composite film material.
The data of the performance test of the ternary composite film material of the comparative example are shown in table 1.
Comparative example 3
The preparation method of the purified lignin/organic modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting purified lignin from sulfate lignin by using ethyl acetate as a solvent, performing ball milling and drying, modifying montmorillonite by using Cetyl Trimethyl Ammonium Bromide (CTAB) as a modification reagent to obtain organic modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the organic modified montmorillonite and the PBAT, adding 40 parts of PBAT into an open mill, simultaneously adding 30 parts of the organic modified montmorillonite and 30 parts of the purified lignin, and mixing to obtain the purified lignin/organic modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/organic modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The data of the performance test of the ternary composite film material of the comparative example are shown in table 1.
Comparative example 4
The preparation method of the purified lignin/silane modified montmorillonite/PBAT composite film material comprises the following steps:
(1) extracting and purifying lignin from alkali lignin by using ethyl acetate as a solvent, performing ball milling and drying, modifying montmorillonite by using gamma-aminopropyltriethoxysilane (KH550) as a modifying reagent to obtain silane modified montmorillonite, and performing ball milling and drying; drying the purified lignin, the silane modified montmorillonite and the PBAT, adding 40 parts of PBAT into an internal mixer, simultaneously adding 30 parts of silane modified montmorillonite and 30 parts of purified lignin, and mixing to obtain the purified lignin/silane modified montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained purified lignin/silane modified montmorillonite/PBAT composite master batch to obtain a purified lignin/montmorillonite/PBAT composite film material.
The data of the performance test of the ternary composite film material of the comparative example are shown in table 1.
Comparative example 5
The preparation method of the montmorillonite/PBAT composite film material comprises the following steps:
(1) drying the PBAT and the montmorillonite, then adding 70 parts of PBAT and 30 parts of montmorillonite into an open mill, and mixing to obtain the montmorillonite/PBAT composite material master batch.
(2) And carrying out hot pressing film forming on the obtained montmorillonite/PBAT composite material master batch to obtain the montmorillonite/PBAT composite film material.
The data of the performance test of the ternary composite film material of the comparative example are shown in table 1.
The morphology of the quenched section of the ternary composite thin film material in the comparative example observed by SEM is shown in the attached figure 4. From the attached figure 4, it is obvious that cracks and gaps exist between the montmorillonite phase and the PBAT phase, and a 'brick-like wall' structure is not formed, which shows that the addition of lignin has a key role as an adhesion enhancing phase in the ternary composite film material.
Comparative example 6
The preparation method of the lignin/montmorillonite/PBAT composite film material comprises the following steps:
(1) and drying the prehydrolysis liquid lignin, the PBAT and the montmorillonite, then adding 70 parts of PBAT into an open mill, and simultaneously adding 20 parts of montmorillonite and 10 parts of prehydrolysis liquid lignin for mixing to obtain the lignin/montmorillonite/PBAT composite master batch.
(2) And carrying out hot pressing film forming on the obtained lignin/montmorillonite/PBAT composite master batch to obtain the lignin/montmorillonite/PBAT composite film material.
The data of the performance test of the ternary composite film material of the comparative example are shown in table 1.
The morphology of the quenched section of the ternary composite thin film material in the comparative example observed by SEM is shown in the attached figure 5. As can be seen from the attached figure 5, the cracks and gaps between the montmorillonite phase and the PBAT phase are occupied by lignin, and the phenomena of wire drawing and adhesion appear; but the adhesion enhancing effect of the unpurified lignin is not very significant.
Performance test method
And (3) mechanical property detection: determination of tensile Properties of plastics according to the national Standard GB/T1040.2-2006 part 2: test conditions for molded and extruded plastics the mechanical properties of all the above composite film materials were measured, and at least 5 measurements were taken per sample, and the average was taken.
And (3) detecting gas barrier property: the oxygen permeability and the water vapor permeability of all the composite film materials are measured according to the GB/T1038-2000 plastic film and sheet gas permeability test method pressure differential method and the GB/T1037-1988 plastic film and sheet water vapor permeability test method cup method of the national standard, each sample needs to be measured for at least 3 times, and the average value is taken.
The mechanical properties and the oxygen and water vapor transmission data of all the above ternary composite film materials are shown in table 1.
TABLE 1 Performance test data for each of the examples and comparative examples
Remarking: a represents the oxygen transmission coefficient PgUnit 10-14 cm3·cm/(cm2s.Pa); b represents a water vapor transmission coefficient PvUnit 10-13 g·cm/cm2·s·Pa
As shown in the test data in Table 1, the technical scheme of the invention adopts purified lignin, montmorillonite and PBAT to carry out mixing step by step, the PBAT and the montmorillonite are mixed firstly, and then the purified lignin is added for mixing, so that the composite material has good mechanical property (the tensile strength is more than or equal to 13MPa, the elongation at break is more than or equal to 200%) and good gas barrier property (the water vapor permeability coefficient P is more than or equal to 200%) and can be obtainedv≤1.4×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤1.0×10-14 cm3·cm/(cm2S.pa)); furthermore, after montmorillonite is modified, the performance of the film material obtained by the technical scheme of the invention can be further improved, under the condition that the filler in PBAT reaches 60%, the tensile strength can reach more than 20 MPa, the elongation at break can reach more than 222%, and the water vapor permeability coefficient P isv≤1.13×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤0.68×10-14 cm3·cm/(cm2s.Pa); furthermore, when the montmorillonite is modified by adopting silane, the performance of the film material obtained by the technical scheme of the invention can be further improved, the tensile strength can reach more than 21.5Mpa and the elongation at break can reach more than 290% under the condition that the filler in the PBAT reaches 60%, and the water vapor permeability coefficient P isv≤0.91×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤0.62×10-14 cm3·cm/(cm2·s·Pa)。
As can be seen from the test data shown in Table 1, when the one-step mixing process is adopted, even if the mixing time is doubled, the performance of the obtained composite material still cannot meet the use requirement of the material.
Further, the results of FIGS. 1 to 5 are shown and shown in the table1, the charging sequence in the mixing process can influence the construction of the brick-like wall structure of the invention, and further influence the mechanical properties of the material. Compared with the process of simultaneously adding montmorillonite and lignin for mixing, the mechanical strength and the elongation at break of the composite material are greatly improved, which indicates that montmorillonite is primarily and uniformly dispersed in PBAT in the processing process, and lignin is added in the second step, so that the better effect can be generated by filling the gap between montmorillonite phase and PBAT phase; presumably, the reason for this is that the 'step mixing' method can avoid the lignin from wrapping the surface of the montmorillonite and not covering the action structure or group of the montmorillonite, so that the montmorillonite can be uniformly dispersed in the PBAT phase; and then adding purified lignin for mixing, so that the lignin is filled in a gap between the montmorillonite and the PBAT to serve as a third phase for adhesion reinforcement, a brick-like wall structure is constructed, the mechanical property is improved, and the mechanical property of the PBAT can still meet the use requirement under the condition that the filler reaches 60%. The structure of the brick-like wall structure is schematically shown in figure 6, wherein
Which represents a montmorillonite clay,
which represents the amount of lignin,
the PBAT is represented.
Furthermore, the lignin/montmorillonite/PBAT ternary composite film material not only shows excellent mechanical property, but also shows excellent gas barrier property, and the oxygen transmission coefficient of the pure PBAT material is 9.02 multiplied by 10-14cm3·cm/(cm2s.Pa), water vapor transmission coefficient of 2.24X 10-13 g·cm/cm2s.Pa, the oxygen permeability coefficient and the water vapor permeability coefficient of the ternary composite film material obtained by the technical scheme of the invention are greatly reduced, which shows that the ternary composite film material has the advantages of oxygen and water vapor permeabilityHas ultrahigh barrier capability, and can reduce water loss in soil when being used as an agricultural mulching film material.
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the ternary composite film material is characterized by comprising the following steps of:
1-1) drying PBAT and montmorillonite and then mixing together to obtain a first master batch;
1-2) purifying, drying and ball-milling the lignin, and mixing the lignin and the first master batch together to obtain a second master batch; wherein the lignin purification is to purify the lignin by using an organic solvent;
1-3) carrying out hot press molding on the second master batch to obtain a ternary composite film material; the ternary composite film material comprises the following components in percentage by mass: 40-50% of PBAT, 25-30% of montmorillonite and 25-30% of lignin.
2. The method of preparation according to claim 1, characterized in that said lignin purification comprises the following steps:
2-1) dissolving lignin in an organic solvent, and carrying out a first reaction under the condition of stirring;
2-2) filtering the reaction product, taking the filtrate, performing rotary evaporation to recover the organic solvent, wherein the rest substance in the filtrate is the purified lignin.
3. The method of claim 2, wherein the lignin is selected from at least one of alkali lignin, prehydrolysis liquid lignin, and kraft lignin; the organic solvent is selected from at least one of methanol, ethanol and ethyl acetate.
4. The preparation method of claim 1, wherein the montmorillonite is modified montmorillonite, and the modification steps are as follows: dispersing montmorillonite in distilled water, and adding long-chain alkyl quaternary ammonium salt to perform a second reaction; after the reaction is finished, washing with distilled water to remove unreacted reagents, filtering, drying and ball-milling; or hydrolyzing the silane coupling agent, pouring the hydrolysate into the montmorillonite, uniformly stirring, drying and ball-milling.
5. The method according to claim 4, wherein the long-chain alkyl quaternary ammonium salt is at least one selected from the group consisting of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.
6. The method according to claim 4, wherein the silane coupling agent is at least one selected from the group consisting of γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane.
7. The ternary composite film material prepared by the preparation method of claim 1, which is characterized by comprising the following components in percentage by mass: 40-50% of PBAT, 25-30% of montmorillonite and 25-30% of lignin, wherein the lignin is lignin purified by an organic solvent.
8. The ternary composite film material according to claim 7, having a water vapor transmission coefficient Pv≤1.4×10-13 g·cm/cm2s.Pa, oxygen transmission coefficient Pv≤1.0×10-14 cm3·cm/(cm2s.Pa), a tensile strength of not less than 13MPa, and an elongation at break of not less than 200%.
9. The ternary composite film material according to claim 7 or 8, which is produced by the production method according to any one of claims 1 to 6.
10. The application of the ternary composite film material of any one of claims 7 to 9 in the field of agricultural mulching films and packaging materials.
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