CN112552655B - Modified cellulose filled PBAT/PLA composition suitable for preparing film, and preparation and application thereof - Google Patents
Modified cellulose filled PBAT/PLA composition suitable for preparing film, and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a modified cellulose filled PBAT/PLA composition suitable for preparing a film, a preparation method thereof and an application thereof in preparing the film, wherein the composition comprises the following raw materials of a basic component and an additional component; the basic components comprise the following components in parts by weight: 30-80 parts of PBAT, 5-30 parts of PLA and 5-40 parts of modified cellulose; the additional components comprise, based on the total weight of the base component: 1 to 20 weight percent of plasticizer, 1 to 10 weight percent of compatibilizer, 0.1 to 1 weight percent of chain extender and 0.1 to 2 weight percent of lubricant. The preparation method comprises the following steps: uniformly mixing the raw materials according to a ratio, adding the mixture into a double-screw granulator set, extruding and granulating to obtain modified cellulose filled PBAT/PLA particles; the temperature of each section of the double-screw granulator set is 50-200 ℃, and the rotating speed of the screw is 200-550rpm.
Description
Technical Field
The invention relates to the field of biodegradable film materials, in particular to a modified cellulose filled PBAT/PLA composition suitable for preparing a film, and preparation and application thereof.
Background
Biodegradable plastics are a class of plastics that can be caused to degrade by the action of microorganisms that are present in nature. The ideal biodegradable plastic is nontoxic and harmless after being degraded, and has excellent service performance.
The poly (terephthalic acid) -butylene adipate (PBAT) is completely biodegradable aliphatic-aromatic copolyester, has higher elongation at break of more than 700 percent, good flexibility and processability, is widely applied to plastic flexible packaging at present, but the source of the PBAT is still petrochemical engineering, consumes petroleum resources in the production and processing processes and generates more carbon dioxide emission. Polylactic acid (PLA) is a biodegradable material with high strength and high brittleness, which is prepared by using lactic acid obtained by plant fermentation as a raw material through a polymerization mode. The film for packaging prepared by compounding the PBAT and the PLA not only can combine the advantages of the flexibility of the PBAT and the strength of the PLA, but also can improve the biomass source of the composite material and reduce the use of petroleum resources.
At present, the problems of cost and compatibility are firstly solved by compounding PBAT and PLA to prepare the packaging film, a plurality of patents and documents are available at home and abroad for researching the film, and most of fillers used in the film are starch or modified starch. For example, the Chinese patent application with the publication number of CN104861210A discloses a starch-based fully biodegradable resin with stable hydrophobicity and a preparation method thereof, and the raw materials comprise: 20-50 parts of modified starch, 50-80 parts of full-biodegradable polyester, 0.1-5 parts of lubricant and 0.1-0.5 part of antioxidant. The starch is subjected to micronization treatment, then is subjected to high-speed stirring modification, is dried at high pressure and high temperature for 12-24 hours, and then is mixed with the fully biodegradable resin, the lubricant and the antioxidant, and the starch-filled fully biodegradable resin particles with stable hydrophobicity are prepared by granulation through a double-screw extruder. At present, when starch is used as a filler of a film for packaging PBAT/PLA, the problems of long starch treatment time, poor starch plasticizing effect, large influence of moisture on material performance, low comprehensive performance of the material, low productivity and the like still exist.
Cellulose is macromolecular polysaccharide composed of glucose, is insoluble in water and common organic solvents, is the main component of plant cell walls, is a polysaccharide which is widely distributed and has the largest content in nature, and accounts for more than 50% of the carbon content in plants. The current cellulose modification technology mainly focuses on two aspects of etherification and esterification, cellulose is easier to separate from wood fiber through modification, and the prepared modified cellulose, such as carboxymethyl cellulose, hydroxyethyl cellulose and other modified celluloses, are widely applied to industries such as petroleum, food, medicine, textile, papermaking and the like at present, and the cost is relatively low because the modified cellulose industry is mature. The method has certain research value and mass production potential by using cellulose or modified cellulose to replace starch or modified starch as the filler of the film for packaging PBAT/PLA.
At present, there are relatively few patents or literature in this direction. For example, the Chinese patent application with the publication number of CN111057355A discloses a porous cellulose PLA composite material and a preparation method thereof, and the porous cellulose PLA composite material is prepared by taking porous cellulose, PLA, PBAT and an antioxidant as raw materials. The invention mixes and granulates porous cellulose processed by alkali liquor with PLA and PBAT to prepare the fully-degradable composite material, and the composite material can permeate resin matrix into micropores of the porous cellulose to form the physical and mechanical properties of the special-shaped microstructure reinforced composite material due to the existence of the porous fiber. However, the cellulose dried after alkali liquor treatment and ultrasonic cleaning is provided by a laboratory preparation process, so that the industrial extraction difficulty is high and the cost is high.
As disclosed in the chinese invention patent application with publication number CN111286168a, a biodegradable polyester/cellulose composite blown film material and a preparation method thereof, the material comprises the following raw materials in parts by weight: 35-50 parts of PBAT, 8-15 parts of PLA, 10-15 parts of PPC (polypropylene carbonate polyol), 25-35 parts of starch, 20-25 parts of cellulose, 2-5 parts of a compatilizer, 0.01-0.03 part of a chain extender, 1-3 parts of a stabilizer and 1-3 parts of an anti-aging agent. The invention patent not only uses starch and cellulose as fillers to reduce the cost of the film for packaging PBAT/PLA, but also solves the problem of compatibility of PBAT, PLA and biomass fillers by introducing the compatilizer and the chain extender. However, the patent does not describe the extraction process or source of cellulose, and the cost of the unmodified cellulose of the current industrial grade exceeds the price of PBAT resin, so that the aim of reducing the cost cannot be fulfilled.
Disclosure of Invention
In order to improve the biomass content of the PBAT/PLA biodegradable film, reduce the cost, maintain excellent performance and solve the problem of compatibility among materials, the invention provides a modified cellulose filled PBAT/PLA composition suitable for preparing the film. The modified cellulose filled PBAT/PLA biodegradable film prepared from the modified cellulose filled PBAT/PLA composition provided by the invention has the advantages of ensuring the performance, improving the addition amount of the modified cellulose and reducing the cost.
A modified cellulose filled PBAT/PLA composition suitable for use in preparing films, the raw material composition comprising a base component and an additional component;
the basic components comprise the following components in parts by weight:
30-80 parts of PBAT (poly (butylene adipate terephthalate)),
5-30 parts of PLA (polylactic acid),
5-40 parts of modified cellulose;
the additional components include, based on the total weight of the base component:
the modified cellulose is one or more of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose and cellulose acetate butyrate;
the plasticizer is one or more of diethanolamine, triethanolamine, ethylene glycol, glycerol, tripropylene glycol and sorbitol;
the compatibilizer is one or more of ethylene-acrylate-maleic anhydride terpolymer (EMH), ethylene acrylate grafted glycidyl methacrylate (T-GMA), ethylene methyl acrylate grafted glycidyl methacrylate (EMA-GMA), ethylene butyl acrylate grafted glycidyl methacrylate (EBA-GMA), polybutylene succinate grafted glycidyl methacrylate (PBS-g-GMA) and polylactic acid grafted glycidyl methacrylate (PLA-g-GMA);
the chain extender is one or more of KC-3728, ADR-4300-F, ADR-4370-F, ADR-4400 and ADR-4468;
the lubricant is one or more of oleamide, erucamide, ethylene bis stearamide and ethylene bis oleamide.
According to the invention, the addition amount of the modified cellulose filler is increased through the optimized composition and the ratio of the modified cellulose filled PBAT/PLA composition, the production cost is reduced on the premise of ensuring the performance, and the addition amount of biomass of the composition is increased.
In order to enable the composition to be suitable for preparing a film with excellent performance, the invention firstly optimizes the proportion content of each component in a PBAT/PLA/modified cellulose three-component system, and adds a specific amount and a specific kind of functional auxiliary agents such as a plasticizer, a compatibilizer, a chain extender, a lubricant and the like on the basis. Researches find that the specific addition amount and specific types of functional auxiliaries are important for preparing the modified cellulose filled PBAT/PLA composition into a film with excellent comprehensive performance, and each functional auxiliary is not necessary.
Cellulose is a natural polymer, and is difficult to separate from plants and directly process into products due to high crystallinity, water insolubility and no fixed melting point. The invention adopts the specific modified cellulose matured on the market, and further modification or treatment is not needed.
The plasticizer can plasticize the modified cellulose to ensure that the modified cellulose filler has certain plasticity, so that the addition proportion of the modified cellulose in a composition system can be increased and the excellent performance of a product can be ensured.
Because solubility parameters of PBAT and PLA are greatly different, the PBAT and PLA are directly blended to cause phase separation of the prepared composite material, so that the blow-molded modified cellulose filled PBAT/PLA biodegradable film has poor performance, obvious layering occurs, and even film forming cannot be performed. The compatibilizer effectively improves the interfacial compatibility of PBAT and PLA, thereby ensuring that the modified cellulose filled PBAT/PLA biodegradable film with better performance is prepared.
On the basis of adding the compatibilizer, the chain extender of a specific kind is further added to effectively initiate the chain extension reaction of PLA, so that the interfacial compatibility of PBAT/PLA/modified cellulose is further improved.
Aiming at the composition system of the invention, the amide lubricant is added to reduce the friction heat between materials and reduce the thermal degradation of the composition, thereby improving the processing performance of the PBAT/PHA/wood flour composition during granulation. Meanwhile, the amide lubricant has the effect of preventing adhesive patches in the composition system of the invention, and can also improve the antistatic property of plastic products.
With the aid of the functional additives, the modified cellulose filled PBAT/PLA composition can still be suitable for preparing high-performance films under the condition of containing higher content of modified cellulose and biomass.
Preferably, the weight average molecular weight of the PBAT is 50000-80000, and the weight average molecular weight range is found to enable the PBAT/PHA/wood flour completely biodegradable film prepared from the composition to have higher flexibility.
It was found that the melt flow rate of the particles during the blow molding process into films has a large influence on the process stability. Preferably, the melt flow rate of the PBAT under the load of 2.16kg and the temperature of 190 ℃ is 1-10g/10min, which is beneficial to ensuring that the PBAT can stably and continuously blow-molded into films in the blow-molding processing process and simultaneously ensures that the thickness of the films is uniform.
The PBAT is preferably one or more of C1100, C1200, C2224, BX7011, BX8145 and TH 801T.
The PLA preferably has one or more of the grades 2003D, 4032D, 4033D, 4044D and 4060D, and the modified cellulose filled PBAT/PLA biodegradable film prepared from the composition has higher strength and better processing performance.
In the above preferred case, in order to adapt to the high addition amount of modified cellulose and biomass, the modified cellulose-filled PBAT/PLA composition comprises the following basic components in parts by weight:
30-70 parts of PBAT (poly (butylene adipate-co-terephthalate)),
5-20 parts of PLA (polylactic acid),
10-40 parts of modified cellulose,
the additional components include, based on the total weight of the base component:
the invention also provides a preparation method of the modified cellulose filled PBAT/PLA composition, which comprises the steps of uniformly mixing the raw materials according to a ratio, adding the mixture into a double-screw granulator set, extruding and granulating to obtain modified cellulose filled PBAT/PLA particles;
the temperature of each section of the double-screw granulator set is 50-200 ℃, and the screw rotating speed is 200-550rpm.
The mixture can be stirred and mixed for 10-20min at normal temperature by adopting a high-speed mixer.
The invention also provides the modified cellulose filled PBAT/PLA particle prepared by the preparation method of the modified cellulose filled PBAT/PLA composition.
The invention also provides a preparation method of the modified cellulose filled PBAT/PLA biodegradable film, wherein a film blowing machine is used for blowing the modified cellulose filled PBAT/PLA particles into a film;
the temperature of each section of a screw of the film blowing machine is 100-180 ℃, and the temperature of a die head is 130-190 ℃.
The invention also provides the modified cellulose filled PBAT/PLA biodegradable film prepared by the preparation method.
The invention also provides application of the modified cellulose filled PBAT/PLA composition in preparation of a film.
Compared with the prior art, the invention has the main advantages that:
1. the invention provides a modified cellulose filled PBAT/PLA composition and a proportion thereof, wherein a modified cellulose filler is added into the PBAT/PLA fully-degradable composition, so that the biomass source ratio is improved, and the use of petroleum resources PBAT in the composition is reduced.
2. The biomass filler adopts the modified cellulose, so that the problem of high cost of the cellulose as the PBAT/PLA composition filler is solved, and the cost is further reduced.
3. The modified cellulose filled PBAT/PLA biodegradable film prepared from the modified cellulose filled PBAT/PLA composition provided by the invention has the advantages that the cost is reduced, and the excellent performance of the film is ensured.
4. The biodegradable product prepared from the modified cellulose filled PBAT/PLA composition and the modified cellulose filled PBAT/PLA biodegradable film provided by the invention has excellent plastic performance, and is suitable for various packaging products.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
All the raw materials used in the following examples and comparative examples were commercially available except for the specific ones. The weight average molecular weight of PBAT is 50000-80000, and the melt flow rate under a load of 2.16kg and at 190 ℃ is 1-10g/10min.
The performance evaluation mode of the biodegradable film comprises the following steps:
tensile strength, tearing strength, pendulum impact resistance and puncture strength test: and testing according to a corresponding national standard testing method.
And (3) testing tensile property: the test is carried out according to GB/T1040.3-2006, a sample adopts a model 2, the length is 150mm, the width is 15mm, and the test speed is 200mm/min. Detecting data of the sample in the longitudinal direction and the transverse direction;
and (3) testing the tearing strength: the method is carried out according to the specification of GB/T16578.2-2009. Detecting data of the sample in the longitudinal direction and the transverse direction;
pendulum impact resistance: testing according to GB/T8809-2015 standard;
puncture strength: testing according to GB/T10004-2008 standard;
the tensile strength unit is MPa, the elongation at break unit is%, the right-angle tearing force unit is N, the pendulum impact resistance unit is J, and the puncture strength unit is N.
Example 1
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT BX7011 wt%, PLA 2003D 10wt%, carboxymethyl cellulose 22wt%, sorbitol 8wt%, EMH 4wt%, ADR-4370-F0.1 wt%, and ethylene bisoleamide 0.9wt%.
Example 2
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT C1200 wt%, PLA 4033D 10wt%, ethylcellulose 30wt%, triglycerol 4.5wt%, T-GMA 3wt%, ADR-4468 0.3wt%, erucamide 0.2wt%.
Example 3
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT C1100 wt%, PLA 4032D 5wt%, methylcellulose 20wt%, ethylene glycol 3.5wt%, EMA-GMA 4wt%, ADR-4300-F0.2 wt%, erucamide 0.3wt%.
Example 4
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT BX8145 wt%, PLA 4060D 10wt%, carboxymethyl cellulose 23wt%, triethanolamine 8wt%, EMH 3wt%, KC-3728 0.1wt%, and ethylene bisoleamide 0.9wt%.
Example 5
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT TH801T 40wt%, PLA 4044D 10wt%, hydroxypropyl methyl cellulose 40wt%, glycerol 6wt%, PLA-g-GMA 3.5wt%, ADR-4400.2wt%, and oleamide 0.3wt%.
Example 6
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT C2224 wt%, PLA 4060D 5wt%, hydroxyethyl cellulose 32.5wt%, sorbitol 10wt%, PBS-g-GMA 1wt%, ADR-4370-F0.5 wt%, and oleamide 1wt%.
Example 7
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT C1200 wt%, PLA 4044D 20wt%, ethyl cellulose 40wt%, diethanolamine 7.5wt%, PBS-g-GMA 2wt%, ADR-4468 0.2wt%, and oleamide 0.3wt%.
Example 8
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT C1200 wt%, PLA 2003D 12wt%, cellulose acetate butyrate 30wt%, triglycerol 3.5wt%, EBA-GMA 4wt%, ADR-4400.3wt%, oleamide 0.2wt%.
Example 9
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT C1200 wt%, PLA 4033D 15wt%, hydroxypropyl methylcellulose 15wt%, triglycerol 4.5wt%, T-GMA 2wt%, ADR-4468.3wt%, erucamide 0.2wt%.
Example 10
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT BX8145 wt%, PLA 4032D 20wt%, hydroxyethyl cellulose 10wt%, diethanolamine 1wt%, T-GMA 4wt%, KC-3728 0.3wt%, and ethylene bisstearamide 0.7wt%.
Comparative example 1
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT BX7011 wt%, PLA 2003D 32wt%, carboxymethyl cellulose 42wt%, sorbitol 0.5wt%, EMH 11wt%, ADR-4370-F2 wt%, ethylene bisoleamide 2.5wt%.
Comparative example 2
The modified cellulose filled PBAT/PLA composition takes the total weight of the modified cellulose filled PBAT/PLA composition as a reference, and comprises the following raw materials:
PBAT BX7011 wt%, PLA 2003D 10wt%, EMH 4wt%, ADR-4370-F0.1 wt%, and ethylene bisoleic acid amide 0.9wt%.
The components shown in examples 1-10 and comparative examples 1-2 were prepared according to the following procedure:
(1) Stirring all the components in a high-speed mixer at normal temperature for 18 minutes;
(2) Extruding and granulating by using a parallel double-screw granulator set to obtain modified cellulose filled PBAT/PLA particles; wherein, the temperature of each section of the double-screw granulator set is as follows: first zone 70 deg.C, second zone 120 deg.C, third zone 140 deg.C, fourth zone 150 deg.C, fifth zone 160 deg.C, sixth zone 165 deg.C, seventh zone 170 deg.C, eighth zone 175 deg.C, ninth zone 170 deg.C, tenth zone 165 deg.C, and head 160 deg.C; setting the screw rotation speed to 350rpm;
(3) Use inflation film manufacturing machine, wherein, each district temperature of inflation film manufacturing machine is: the first zone 120 ℃, the second zone 145 ℃, the third zone 155 ℃, the tee-down 165 ℃, the tee-up 165 ℃, the die-down 165 ℃ and the die-up 175 ℃ are controlled to make the thickness of the film 60 +/-5 μ M, and the biodegradable films are marked as M1-M10 (corresponding to examples 1-10) and D1-D2 (corresponding to comparative examples 1-2), respectively.
The above M1-10 and D1-2 were tested and the results are shown in Table 1 below.
TABLE 1
The composition of comparative example D1 is outside the scope of the invention; comparative example D2 is without modified cellulosic filler and plasticizer. As can be seen from the data in Table 1, the comparative example D1 has large differences from M1 to M10 and D2 in various properties, and has the phenomena of uneven discharging and strip breakage in the granulation process, and air leakage and bubble breakage in the film blowing process, which indicates that the addition amount of the composition of D1 is not suitable for preparing the modified cellulose filled PBAT/PLA biodegradable film.
As can be seen from the data in Table 1, compared with the comparative example D2, the modified cellulose added examples M1-M10 have slight loss of the performance of the PBAT/PLA biodegradable film filled with the modified cellulose, but are all within a reasonable range, which is the reason for the combined action of the functional additives including the plasticizer in the invention, so that the film still has good performance under high content of the modified cellulose and biomass. Therefore, the modified cellulose filled PBAT/PLA biodegradable film has excellent performance, each mechanical property index meets the requirement of practical application, and the modified cellulose filled PBAT/PLA biodegradable film is suitable for various packaging products, in particular for various packaging bags and/or sealing bags.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (7)
1. A modified cellulose filled PBAT/PLA composition suitable for use in the preparation of films, wherein the raw material composition comprises a base component and an additional component;
the basic components comprise the following components in parts by weight:
30-80 parts of PBAT (poly (butylene adipate terephthalate)),
5-30 parts of PLA (polylactic acid),
5-40 parts of modified cellulose;
the additional components include, based on the total weight of the base component:
the weight average molecular weight of the PBAT is 50000-80000, and the melt flow rate under the load of 2.16kg and the temperature of 190 ℃ is 1-10g/10min;
the modified cellulose is one or more of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose and cellulose acetate butyrate;
the plasticizer is one or more of diethanolamine, triethanolamine, ethylene glycol, tripropylene glycol and sorbitol;
the compatibilizer is one or more of ethylene-acrylate-maleic anhydride terpolymer, ethylene acrylate grafted glycidyl methacrylate, ethylene methyl acrylate grafted glycidyl methacrylate, ethylene butyl acrylate grafted glycidyl methacrylate and polybutylene succinate grafted glycidyl methacrylate;
the chain extender is one or more of KC-3728, ADR-4300-F, ADR-4370-F, ADR-4400 and ADR-4468;
the lubricant is one or more of oleamide and erucamide.
2. The modified cellulose filled PBAT/PLA composition of claim 1, wherein the base component comprises, in parts by weight:
30-70 parts of PBAT (poly (butylene adipate terephthalate)),
5-20 parts of PLA (polylactic acid),
10-40 parts of modified cellulose, namely,
the additional components include, based on the total weight of the base component:
3. the preparation method of the modified cellulose filled PBAT/PLA composition according to claim 1 or 2, characterized in that the raw materials are uniformly mixed according to the proportion and then added into a twin-screw granulator set for extrusion and granulation to obtain modified cellulose filled PBAT/PLA particles;
the temperature of each section of the double-screw granulator set is 50-200 ℃, and the screw rotating speed is 200-550rpm.
4. The modified cellulose filled PBAT/PLA particle prepared by the preparation method of claim 3.
5. A preparation method of a modified cellulose filled PBAT/PLA biodegradable film is characterized in that a film blowing machine is used for blowing the modified cellulose filled PBAT/PLA particles of claim 4 into a film;
the temperature of each section of a screw of the film blowing machine is 100-180 ℃, and the temperature of a die head is 130-190 ℃.
6. A modified cellulose filled PBAT/PLA biodegradable film prepared according to the preparation method of claim 5.
7. Use of a modified cellulose filled PBAT/PLA composition according to claim 1 or 2 for the preparation of a film.
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| WO2023209703A1 (en) * | 2022-04-27 | 2023-11-02 | Tipa Corp. Ltd | Biodegradable sheets |
| KR20230164563A (en) * | 2022-05-25 | 2023-12-04 | 주식회사 엘지화학 | Resin composition and molded article |
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