CN114524958B - Preparation method of degradable barrier film - Google Patents
Preparation method of degradable barrier film Download PDFInfo
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- CN114524958B CN114524958B CN202210256837.7A CN202210256837A CN114524958B CN 114524958 B CN114524958 B CN 114524958B CN 202210256837 A CN202210256837 A CN 202210256837A CN 114524958 B CN114524958 B CN 114524958B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a preparation method of a degradable barrier film, which comprises the following steps: firstly, modifying montmorillonite by ball milling with isocyanate to ensure that-NCO at one end of the isocyanate is connected with-OH of the montmorillonite, and more layers can be stripped; then dispersing the isocyanate modified montmorillonite in a mixed solution of toluene and methylene dichloride to form a suspension, adding pentaerythritol to enable-OH to react with-NCO at the other end of the isocyanate, and then adding polycaprolactone to generate a similar claw, so that the montmorillonite is favorable for tightly grasping the PBAT matrix. The polycaprolactone density around the montmorillonite is higher, the interaction force of the montmorillonite and the PBAT is greatly improved, the problem of poor dispersibility of the montmorillonite in the PBAT is well solved, a perfect network can be formed between the montmorillonite and the PBAT matrix and between the montmorillonite, and the barrier property of the composite membrane is greatly improved.
Description
Technical Field
The invention relates to the technical field of films, in particular to a preparation method of a degradable barrier film.
Background
With the development of plastic industry, plastic films are widely applied, and products such as plastic bags, plastic mulch films, packaging bags and the like improve logistics efficiency, increase agricultural production benefits and greatly facilitate the life of people. However, at the same time, because the plastic film is disposable, great "white pollution" pressure is brought to the environment every year, most of plastic films are polyethylene, polypropylene and the like with molecular weight of tens of thousands to hundreds of thousands, and the plastic films are difficult to degrade in nature. These tiny thin film fragments (i.e., microplastic) float in the air, or enter the respiratory system of the living being, or stick to the surface of the food and enter the digestive system, accumulating in the living being over time and causing disease; microplastic may also be deposited in the soil, resulting in impeded flow of water and gas fertilizer in the soil, hardened soil, and affected crop yields. Therefore, the problem of plastic film pollution is of great importance to life of people, and research on degradable films is carried out.
The PBAT is formed by copolymerizing terephthalic acid, adipic acid and butanediol, is an excellent biodegradable material, has excellent mechanical property, strong toughness and good processability, and can be blown into a film. Montmorillonite is a kind of soil-like mineral formed by stacking silicate sheets with negative charges on the surface of nanometer thickness by virtue of electrostatic action between layers, and the structure endows montmorillonite with some characteristics such as barrier property. However, montmorillonite is modified in general because of the presence of a large amount of inorganic ions between montmorillonite layers, which is detrimental to dispersion in polymer aggregates. The addition of modified montmorillonite to PBAT is an effective means of improving the barrier properties of PBAT.
Zhu Xiaoqi (Hunan university of industry, 6.5, 4 th month) studied organic montmorillonite modified PBAT in its major paper, and found that the mechanical properties and moisture permeability of PBAT were effectively improved, however, when the montmorillonite content was higher, the phenomenon of slipping of performance occurred.
The patent of CN202111230588.6 discloses a preparation method and application of a biodegradable antioxidant fruit and vegetable preservative film, wherein starch, glycerol, organically modified montmorillonite and quercetin are mixed to obtain modified powder, the modified powder and PBAT are mixed, granulated and blow-molded to obtain the antioxidant preservative film, and the montmorillonite is not further treated, so that the additive content is low and the barrier performance is limited. The patent of CN202110766224.3 discloses a degradable plastic mulch film based on PBAT, which comprises the components of PBAT, PE, iron-based montmorillonite and modified polysiloxane, wherein the iron-based montmorillonite is obtained by reacting sodium modification and ferric stearate, the modified polysiloxane effectively improves the compatibility of the PBAT and PE and separates the montmorillonite to prevent aggregation, but the method has weak dispersing acting force on the montmorillonite and contains heavy metal.
Therefore, there is a need to find a method for effectively dispersing montmorillonite in PBAT, which is nontoxic and free of heavy metals, and improves the barrier property of PBAT membranes.
Disclosure of Invention
The invention aims to provide a preparation method of a degradable barrier film, wherein a perfect network can be formed between montmorillonite and PBAT matrix and between montmorillonite, and the barrier performance of the composite film is greatly improved.
In order to achieve the above object, the present invention adopts the following technical scheme:
a method of making a degradable barrier film comprising the steps of:
(1) Stripping, mixing and reacting montmorillonite and isocyanate in a ball mill;
(2) Dispersing the product obtained in the step (1) in a mixed solution of dichloromethane and toluene, adding a dichloromethane solution of pentaerythritol, stirring, adding a dichloromethane solution of polycaprolactone and a catalyst, stirring, washing, filtering and drying;
(3) And (3) mixing the product obtained in the step (2), PBAT and inorganic filler, extruding and granulating by a double screw, and blowing a film.
In the method of the invention, the isocyanate is one or more of hexamethylene isocyanate (HDI), diphenylmethane diisocyanate (MDI), L-Lysine Triisocyanate (LTI) and Toluene Diisocyanate (TDI), and is preferably hexamethylene isocyanate (HDI).
In the method of the invention, in the step (1), under the ball milling action, montmorillonite sheets are peeled off to generate thinner and more sheets, which is more beneficial to the construction of montmorillonite inorganic barrier layers in the film forming process.
In the step (1), the ball milling time is 1-6h, preferably 2-4h.
In step (1) according to the invention, the isocyanate represents 1 to 10% by weight, preferably 3 to 5% by weight, of the montmorillonite.
In the method of the invention, in the step (2), the volume ratio of the dichloromethane to the toluene in the mixed solution of the dichloromethane and the toluene is 5:5-9:1.
In the step (2), the dispersion ratio of the product of the step (1) in the mixed solution is 1-10wt%.
In the method of the invention, in the step (2), in the dichloromethane solution of pentaerythritol, pentaerythritol accounts for 0.01-0.1wt% of dichloromethane.
In the method of the present invention, in the step (2), the volume ratio of the dichloromethane solution of pentaerythritol to the mixed solution of dichloromethane and toluene is 1:5-3:5.
In the method of the invention, in the step (2), the polycaprolactone accounts for 0.1-1wt% of the dichloromethane in the dichloromethane solution of the polycaprolactone.
In the method of the present invention, in the step (2), the volume ratio of the dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene is 1:5-3:5.
In the method, the catalyst is one or more of tetraphenyltin, stannous octoate and dibutyltin dilaurate.
In the method of the invention, the catalyst accounts for 0.01 to 0.05 weight percent of the polycaprolactone.
The inorganic filler is one or more of talcum powder, nano calcium carbonate, mica, chalk powder and nano calcium oxide, preferably talcum powder, and the mesh number of the talcum powder is 6000-8000.
In the step (3), the components in parts by weight are as follows: 70-90 parts of PBAT, 5-20 parts of the product obtained in the step (2) and 1-10 parts of inorganic filler.
In the step (3), in the extrusion granulation process, the screw process parameters are that the temperature of a charging barrel is 150-190 ℃, the rotating speed of the screw is 200-600rpm, and the feeding frequency is 5-10; preferably, the temperature of the charging barrel is 160-170 ℃, the rotating speed of the screw is 300-400rpm, and the feeding frequency is 6-8.
In the step (3), in the film blowing process, the working parameters of a film blowing machine are as follows: the heating temperature is 150-190 ℃, the rotating speed of the screw is 25-50rpm, and the traction speed is 3-6m/min; preferably, the heating temperature is 160-170 ℃, the screw rotating speed is 30-40rpm, and the traction speed is 4-5m/min.
As a preferable scheme, in the step (3) of the invention, 5-15wt% of PBAT opening agent master batch is added into the granules obtained by granulation in the film blowing process, wherein the opening agent is preferably erucamide, and the opening agent accounts for 5-15wt% of the master batch.
The key point of the montmorillonite modification method is that isocyanate is utilized to modify montmorillonite, more sheets are stripped by ball milling, the-NCO at one end of isocyanate is connected with the-OH in the montmorillonite in a reaction way, the-NCO at the other end is connected with one-OH in pentaerythritol, and the other three-OH are connected with polycaprolactone molecular chains to form a claw. Because polycaprolactone and PBAT have good compatibility, and the claw-shaped structure is favorable for grasping the PBAT matrix, the montmorillonite modification step greatly improves the compatibility between the PBAT matrix and the PBAT, improves the dispersibility of the montmorillonite in the resin, and avoids agglomeration and the generation of defects.
The patent utilizes ball milling external force to strip and modify montmorillonite sheets through mixing and ball milling isocyanate and montmorillonite, the stripped montmorillonite reacts with pentaerythritol and polycaprolactone successively to form claw-shaped objects, the modified montmorillonite, PBAT and inorganic filler are blended, extruded and granulated, and the high-barrier PBAT film containing montmorillonite can be obtained by blowing a film. Under the action of ball milling, montmorillonite sheets are stripped, the thinning number of the sheets is increased, and more montmorillonite sheets can be obtained in unit area when the sheets are dispersed in PBAT. In addition, the molecular chain of polycaprolactone on the montmorillonite improves the interaction force between the molecular chain and the PBAT matrix, is favorable for uniform dispersion of the montmorillonite, reduces agglomeration or defect generation, and greatly improves the barrier property of the PBAT.
The invention provides a preparation method of a degradable barrier film, which has the following beneficial effects:
(1) The montmorillonite modified by the isocyanate, the pentaerythritol and the polycaprolactone is a claw-shaped structure connected with the montmorillonite, the claw-shaped structure has good compatibility with the PBAT, and compared with a single molecular chain, the claw-shaped structure has larger interaction force on a matrix, so that the montmorillonite is very beneficial to the dispersion and the adhesion of the montmorillonite in the matrix, and the construction of a montmorillonite barrier network is effectively assisted.
(2) The ball milling can peel off montmorillonite layers, so that the quantity of montmorillonite in unit area is increased, and the barrier property is effectively improved. The stripping degree can be controlled by changing the ball milling time, and the blocking effect is controlled.
(3) The gaps among the montmorillonite are filled with talcum powder with high mesh number, so that water vapor and the like are less likely to penetrate through the film, and the barrier property is further improved. Can be widely applied to the fields of packaging, express bags, adhesive tapes, mulching films and the like.
Detailed Description
The following examples further illustrate preferred embodiments within the scope of the invention. The examples are merely illustrative and not limiting of the scope of the invention, as many variations of the invention are possible without departing from its spirit and scope.
In the following examples, the equipment information used is as follows:
ball mill: nanjing Chi Seiki scientific development Co., ltd., QM-3SP04L.
High-speed mixer: suzhou pine far environmental protection technology Co., ltd., SHR-50L.
Twin screw extruder: nanjing Rate extrusion machinery Co., ltd., RXT26-900-22-58.
Film blowing machine: lebetaceae, LF400.
Example 1
Hexamethylene isocyanate accounting for 5wt% of montmorillonite is mixed with montmorillonite, then the mixture is operated for 2 hours in a ball mill, the montmorillonite is taken out and then dispersed in a mixed solution of methylene dichloride and toluene (the volume ratio of the methylene dichloride to the toluene is 6:4), and the montmorillonite accounts for 5wt%. Adding a dichloromethane solution in which 0.08wt% of pentaerythritol is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of pentaerythritol to the mixed solution of dichloromethane and toluene is 2:5, stirring for 2 hours, adding dichloromethane in which 0.8wt% of polycaprolactone (catalyst tetraphenyltin accounts for 0.04wt% of polycaprolactone) is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene is 2:5, and stirring for 2 hours. Filtering after the reaction is finished, and drying for 2 hours at 80 ℃ to obtain the dried modified montmorillonite. Mixing the modified montmorillonite with PBAT and 7000 mesh talcum powder, and counting the components: 85 parts of PBAT, 10 parts of modified montmorillonite and 5 parts of talcum powder. And (3) extruding and granulating by a double-screw extruder after mixing, wherein the processing temperature of the extruder is 170 ℃, the rotating speed is 300 and the feeding frequency is 8. Film blowing is carried out by a film blowing machine, the heating temperature is 165 ℃, the rotating speed of a screw is 35, and the traction speed is 5m/min.
Example 2
Hexamethylene isocyanate accounting for 2wt% of montmorillonite is mixed with montmorillonite, then the mixture is operated for 2 hours in a ball mill, the montmorillonite is taken out and then dispersed in a mixed solution of methylene dichloride and toluene (the volume ratio of the methylene dichloride to the toluene is 6:4), and the montmorillonite accounts for 5wt%. Adding a dichloromethane solution in which 0.04wt% of pentaerythritol is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of pentaerythritol to the mixed solution of dichloromethane and toluene is 2:5, stirring for 2 hours, adding dichloromethane in which 0.4wt% of polycaprolactone (catalyst tetraphenyltin accounts for 0.04wt% of polycaprolactone) is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene is 2:5, and stirring for 2 hours. Filtering after the reaction is finished, and drying for 2 hours at 80 ℃ to obtain the dried modified montmorillonite. Mixing the modified montmorillonite with PBAT and 7000 mesh talcum powder, and counting the components: 85 parts of PBAT, 10 parts of modified montmorillonite and 5 parts of talcum powder. And (3) extruding and granulating by a double-screw extruder after mixing, wherein the processing temperature of the extruder is 170 ℃, the rotating speed is 300 and the feeding frequency is 8. Film blowing is carried out by a film blowing machine, the heating temperature is 165 ℃, the rotating speed of a screw is 35, and the traction speed is 5m/min.
Example 3
Hexamethylene isocyanate accounting for 5wt% of montmorillonite is mixed with montmorillonite, then the mixture is operated for 2 hours in a ball mill, the montmorillonite is taken out and then dispersed in a mixed solution of methylene dichloride and toluene (the volume ratio of the methylene dichloride to the toluene is 6:4), and the montmorillonite accounts for 5wt%. Adding a dichloromethane solution in which 0.08wt% of pentaerythritol is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of pentaerythritol to the mixed solution of dichloromethane and toluene is 2:5, stirring for 2 hours, adding dichloromethane in which 0.8wt% of polycaprolactone (catalyst tetraphenyltin accounts for 0.04wt% of polycaprolactone) is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene is 2:5, and stirring for 2 hours. Filtering after the reaction is finished, and drying for 2 hours at 80 ℃ to obtain the dried modified montmorillonite. Mixing the modified montmorillonite with PBAT and 7000 mesh talcum powder, and counting the components: 85 parts of PBAT, 5 parts of modified montmorillonite and 10 parts of talcum powder. And (3) extruding and granulating by a double-screw extruder after mixing, wherein the processing temperature of the extruder is 170 ℃, the rotating speed is 300 and the feeding frequency is 8. Film blowing is carried out by a film blowing machine, the heating temperature is 165 ℃, the rotating speed of a screw is 35, and the traction speed is 5m/min.
Comparative example 1
Mixing hexamethylene isocyanate accounting for 5wt% of montmorillonite with montmorillonite in a high-speed mixer for 2 hours, taking out the montmorillonite, dispersing the montmorillonite in a mixed solution of dichloromethane and toluene (the volume ratio of dichloromethane to toluene is 6:4), and accounting for 5wt% of the montmorillonite. Adding a dichloromethane solution in which 0.08wt% of pentaerythritol is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of pentaerythritol to the mixed solution of dichloromethane and toluene is 2:5, stirring for 2 hours, adding dichloromethane in which 0.8wt% of polycaprolactone (catalyst tetraphenyltin accounts for 0.04wt% of polycaprolactone) is dissolved into the mixed solution, wherein the volume ratio of the dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene is 2:5, and stirring for 2 hours. Filtering after the reaction is finished, and drying for 2 hours at 80 ℃ to obtain the dried modified montmorillonite. Mixing the modified montmorillonite with PBAT and 7000 mesh talcum powder, and counting the components: 85 parts of PBAT, 10 parts of modified montmorillonite and 5 parts of talcum powder. And (3) extruding and granulating by a double-screw extruder after mixing, wherein the processing temperature of the extruder is 170 ℃, the rotating speed is 300 and the feeding frequency is 8. Film blowing is carried out by a film blowing machine, the heating temperature is 165 ℃, the rotating speed of a screw is 35, and the traction speed is 5m/min.
Comparative example 2
The montmorillonite is operated in a ball mill for 2 hours, and after being taken out, the montmorillonite is mixed with PBAT and 7000 mesh talcum powder, and the components are counted: 85 parts of PBAT, 10 parts of montmorillonite and 5 parts of talcum powder. And (3) extruding and granulating by a double-screw extruder after mixing, wherein the processing temperature of the extruder is 170 ℃, the rotating speed is 300 and the feeding frequency is 8. Film blowing is carried out by a film blowing machine, the heating temperature is 165 ℃, the rotating speed of a screw is 35, and the traction speed is 5m/min.
Comparative example 3
Hexamethylene isocyanate accounting for 5wt% of montmorillonite is mixed with montmorillonite, then the mixture is operated for 2 hours in a ball mill, the montmorillonite is taken out and then dispersed in a mixed solution of methylene dichloride and toluene (the volume ratio of the methylene dichloride to the toluene is 6:4), and the montmorillonite accounts for 5wt%. Dichloromethane in which 0.8wt% of polycaprolactone (catalyst tetraphenyltin accounting for 0.04wt% of polycaprolactone) was dissolved was added to the mixed solution, and the volume ratio of dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene was 2:5, and stirred for 2 hours. Filtering after the reaction is finished, and drying for 2 hours at 80 ℃ to obtain the dried modified montmorillonite. Mixing the modified montmorillonite with PBAT and 7000 mesh talcum powder, and counting the components: 85 parts of PBAT, 10 parts of modified montmorillonite and 5 parts of talcum powder. And (3) extruding and granulating by a double-screw extruder after mixing, wherein the processing temperature of the extruder is 170 ℃, the rotating speed is 300 and the feeding frequency is 8. Film blowing is carried out by a film blowing machine, the heating temperature is 165 ℃, the rotating speed of a screw is 35, and the traction speed is 5m/min.
The oxygen permeability, moisture permeability and mechanical properties of examples 1 to 3 and comparative examples 1 to 3 were measured, and the results are shown in Table 1. Oxygen transmission rate was tested according to GB/T1038-2000, water vapor transmission rate was tested according to GB/T1037-1988, and mechanical properties were tested according to GB/T29646-2013.
Table 1 test results for examples and comparative examples
It can be seen from Table 1 that the modified montmorillonite has a much better barrier property than the unmodified montmorillonite. The montmorillonite layer stripping brought by ball milling is more beneficial to the barrier effect compared with a high-speed mixer. The grafting degree of the modified group and the proportion of the modified montmorillonite in the matrix can be improved, so that the barrier property can be effectively improved. Pentaerythritol forms a claw-like structure with better barrier properties than polycaprolactone grafts alone.
The above embodiments are only for illustrating the technical concept and features of the present invention, and should not be construed as limiting the scope of the present invention. All changes and modifications that come within the spirit of the invention are desired to be protected.
Claims (13)
1. A method of making a degradable barrier film comprising the steps of:
(1) Stripping, mixing and reacting montmorillonite and isocyanate in a ball mill;
(2) Dispersing the product obtained in the step (1) in a mixed solution of dichloromethane and toluene, adding a dichloromethane solution of pentaerythritol, stirring, adding a dichloromethane solution of polycaprolactone and a catalyst, stirring, washing, filtering and drying;
(3) Mixing the product obtained in the step (2), PBAT and inorganic filler, extruding and granulating by a double screw, and blowing a film;
the isocyanate is one or more of hexamethylene isocyanate, diphenylmethane diisocyanate, L-lysine triisocyanate and toluene diisocyanate.
2. The method of claim 1, wherein in step (1), the isocyanate comprises 1 to 10wt% of the montmorillonite.
3. The method of claim 1, wherein in step (1), the isocyanate comprises 3 to 5wt% of the montmorillonite.
4. The method according to claim 1, wherein in the step (2), the volume ratio of dichloromethane to toluene in the mixed solution of dichloromethane and toluene is 5:5-9:1; the product of the step (1) is dispersed in the mixed solution at a ratio of 1-10wt%.
5. The method according to claim 1, wherein in the step (2), pentaerythritol is 0.01 to 0.1wt% of methylene chloride in a methylene chloride solution of pentaerythritol; the volume ratio of the dichloromethane solution of pentaerythritol to the mixed solution of dichloromethane and toluene is 1:5-3:5.
6. The method according to claim 1, wherein in step (2), polycaprolactone comprises 0.1 to 1wt% of dichloromethane in the dichloromethane solution of polycaprolactone; the volume ratio of the dichloromethane solution of polycaprolactone to the mixed solution of dichloromethane and toluene is 1:5-3:5.
7. The method of claim 1, wherein the inorganic filler is one or more of talc, nano calcium carbonate, mica, chalk powder, nano calcium oxide.
8. The method of claim 1, wherein the inorganic filler is talc having a mesh size of 6000 to 8000.
9. The method of claim 1, wherein in step (3), the following components are in parts by weight: 70-90 parts of PBAT, 5-20 parts of the product obtained in the step (2) and 1-10 parts of inorganic filler.
10. The method according to claim 1, wherein in the step (3), in the extrusion granulation process, the screw process parameters are that the temperature of the barrel is 150-190 ℃, the screw rotation speed is 200-600rpm, and the feeding frequency is 5-10.
11. The method according to claim 1, wherein in the step (3), in the extrusion granulation process, the screw process parameters are that the temperature of the cylinder is 160-170 ℃, the screw rotation speed is 300-400rpm, and the feeding frequency is 6-8.
12. The method according to claim 1, wherein in the step (3), in the film blowing process, the working parameters of the film blowing machine are as follows: the heating temperature is 150-190 ℃, the screw rotating speed is 25-50rpm, and the traction speed is 3-6m/min.
13. The method according to claim 1, wherein in the step (3), in the film blowing process, the working parameters of the film blowing machine are as follows: the heating temperature is 160-170 ℃, the screw rotating speed is 30-40rpm, and the traction speed is 4-5m/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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