CN112322010A - Plastic color master batch capable of being efficiently biodegraded and preparation method thereof - Google Patents
Plastic color master batch capable of being efficiently biodegraded and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/06—Esters
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
Abstract
The application relates to the field of plastics, and particularly discloses a plastic color master batch capable of being efficiently biodegraded and a preparation method thereof. The plastic color master batch comprises the following raw materials in parts by weight: polylactic acid, polymethyl ethylene carbonate, poly (ethylene terephthalate) diacid, polyethylene lactone, toner, bio-based filler, silane coupling agent and dispersing agent; the preparation method comprises the following steps: mixing and heating polylactic acid, polymethyl ethylene carbonate, polyethylene terephthalate diacid and polyethylene lactone, then adding toner, bio-based filler, silane coupling agent and dispersing agent, putting all the raw materials into extrusion equipment, melting at constant temperature and then extruding. The color master batch with high biodegradation efficiency and excellent comprehensive mechanical properties is prepared by mixing polylactic acid, poly (ethylene terephthalate) and poly (methyl ethylene carbonate).
Description
Technical Field
The application relates to the field of plastics, in particular to a plastic color master batch capable of being efficiently biodegraded and a preparation method thereof.
Background
The color master batch is also called a pigment preparation, consists of three parts of pigment, carrier resin and additive, and is a high-efficiency colorant formed by uniformly dispersing the pigment in a pending resin at a high concentration in a special mode, so the color master batch is also called a pigment concentrate. Biodegradation refers to the biochemical process by which organic material is converted, completely or locally, into water, carbon dioxide, methane, energy and new biomass under the action of microorganisms.
Polylactic acid is a novel biodegradable material which is rapidly developed in recent years, and a product produced by taking polylactic acid as a raw material can be degraded by microorganisms, ultraviolet light and the like in the using process and reduced into monomer lactic acid, so that the polylactic acid has good biocompatibility and degradability. When polylactic acid is used as a carrier of color master batches to produce the high-efficiency degradable material, the comprehensive mechanical property is low due to the over-wide molecular weight distribution of the polylactic acid and the insufficient strength and toughness of the color-conducting master batches.
Disclosure of Invention
In order to improve the comprehensive mechanical property on the premise of ensuring that the color master batch can be efficiently degraded, the application provides the plastic color master batch capable of being efficiently biodegraded and the preparation method thereof.
The application provides a plastic color master batch capable of being efficiently biodegraded and a preparation method thereof, and the following technical scheme is adopted:
in a first aspect, the present application provides a plastic color masterbatch capable of efficient biodegradation, which adopts the following technical scheme:
a plastic color master batch capable of being efficiently biodegraded comprises the following raw materials in parts by weight:
polylactic acid: 43-58 parts;
polymethyl ethylene carbonate: 25-35 parts;
poly (ethylene terephthalate): 22-28 parts;
polyethylene lactone: 2-7 parts;
toner: 20-42 parts;
bio-based filler: 15-18 parts;
silane coupling agent: 2.5-4.5 parts;
dispersing agent: 3-6 parts.
By adopting the technical scheme, the three polymers of polylactic acid, poly (butyl terephthalate) oxalate and poly (methyl ethylene carbonate) all contain a large amount of ester bonds, can be completely biodegraded, and meanwhile, the degradation time of the bio-based filler is short, so that the cross-linking structure of the polymer can be broken, and the color master batch product can be rapidly degraded after being buried in soil; the polyethylene glycol is used for improving the compatibility of the polylactic acid, the polybutylene terephthalate and the polymethyl ethylene carbonate, the interface bonding force is increased, and the comprehensive mechanical property of the masterbatch product is integrally improved; the method improves the performance of the color master batch product on the premise of ensuring that the color master batch material can be efficiently biodegraded, and has great social benefit.
Preferably, the raw material components also comprise polyethylene glycol, and the weight portion of the polyethylene glycol is 8-13 portions.
By adopting the technical scheme, the polyethylene glycol has hydrophilic and lipophilic properties, can be used for modifying poly (butyl terephthalate) oxalate and poly (methyl ethylene carbonate), introduces water-absorbing groups on functional groups of the poly (butyl terephthalate) oxalate and the poly (methyl ethylene carbonate), improves biocompatibility, and active enzyme can permeate into active positions of polymer macromolecules to be hydrolyzed, so that molecular frameworks are broken and decomposed into micromolecular products, and the degradation efficiency of the poly (butyl terephthalate) oxalate and the poly (methyl ethylene carbonate) is improved.
Preferably, the bio-based material is modified starch, and the preparation method of the modified starch comprises the following steps: dissolving starch in absolute ethyl alcohol, adding dodecanoic acid acyl chloride, mixing and stirring uniformly, reacting for 3-5 h at the temperature of 105-115 ℃, cooling, filtering, and drying to obtain the modified starch.
By adopting the technical scheme, the modified starch is used as the filler of the color master batch, the dodecanoic acid acyl chloride is used for modifying the starch, and the fatty acid ester group is introduced, so that the hydrophilic and oleophobic properties of the starch are changed into the hydrophobic and oleophilic properties, the interface bonding capability of the modified starch and the polymer is enhanced, the degradation time of the starch is short, the cross-linked structure of the polymer can be broken, and the color master batch product can be rapidly degraded after being buried in soil.
Preferably, the mass ratio of the polylactic acid to the poly (methyl ethylene carbonate) to the poly (butylene terephthalate) oxalate is 10:6: 5.
By adopting the technical scheme, when the proportion of the polylactic acid, the poly (butylene terephthalate) oxalate and the poly (methyl ethylene carbonate) is limited within the proportion range of 10:6:5, the synergistic effect of the polylactic acid, the poly (butylene terephthalate) oxalate and the poly (methyl ethylene carbonate) is realized, the synergistic effect is realized, and the comprehensive mechanical property of the color master batch can be improved.
Preferably, the silane coupling agent is one or a combination of vinyl silane, amino silane and methacryloxy silane.
By adopting the technical scheme, as the bio-based filler has hydrophilic property and the polymer resin molecules have oleophilic property, the silane coupling agent can be combined with the bio-based filler and the polymer resin molecules, so that the combining capability of each molecular component in the color master batch is enhanced, the connection tightness of each component is improved, the collapse rate of the bio-based filler in the color master batch to the polymer resin is accelerated, and the comprehensive mechanical property of the color master batch is improved.
Preferably, the dispersing agent is prepared by mixing sodium pyrophosphate, carboxymethyl cellulose and sodium alginate according to the mass ratio of 2:1: 3.
By adopting the technical scheme, the mass ratio of the sodium pyrophosphate to the carboxymethyl cellulose to the sodium alginate is limited to 2:1:3, so that the dispersity of the bio-based filler in the color master batch can be integrally improved, the molecular components of each part in the color master batch are uniformly mixed, the collapse of a cross-linking structure of polymer resin by the bio-based filler is accelerated, and the biodegradation rate of the color master batch is improved.
Preferably, the toner is an organic toner.
By adopting the technical scheme, the organic toner has complete color spectrum, bright and bright color and strong adhesion color, does not contain heavy metal components, and belongs to environment-friendly toner.
In a second aspect, the application provides a preparation method of a plastic color master batch capable of being efficiently biodegraded, which adopts the following technical scheme:
a preparation method of plastic color master batch capable of being efficiently biodegraded comprises the following steps:
s1, weighing polylactic acid, polymethyl ethylene carbonate, poly (ethylene terephthalate) and polyethylene lactone in the formula, putting the materials into mixing equipment, heating the materials to the temperature of 180-205 ℃, and reacting the materials for 40-55 min under stirring to obtain a primary mixed material;
s2, sequentially adding the toner, the bio-based filler, the silane coupling agent and the dispersing agent into the primary mixed material, and stirring for 15-20 min to obtain an intermediate mixed material;
s3, placing the intermediate mixture into an extrusion device, setting the temperature to be 120-140 ℃, melting at constant temperature for 30-40 min, and then extruding, cooling and forming.
By adopting the technical scheme, the polylactic acid, the polymethyl ethylene carbonate and the polyethylene diacid are mixed in advance, the compatibility of the polylactic acid, the polymethyl ethylene carbonate and the polyethylene diacid is improved through the polyethylene lactone, the chain segment bonding capability is improved, other components are added into the mixture for melting and extrusion, the bio-based filler can be uniformly dispersed in the color master batch component, the bonding capability of each component is correspondingly improved, and the comprehensive mechanical property of the color master batch is integrally improved.
Preferably, in the step S1, the preliminary mixture further includes polyethylene glycol, and the polyethylene glycol and the polylactic acid, the polymethyl ethylene carbonate, the polybutylene terephthalate oxalate and the polyethylene lactone are simultaneously added to the mixing device to be mixed.
By adopting the technical scheme, the polyethylene glycol is added simultaneously in the mixing process of the polylactic acid, the polymethyl ethylene carbonate, the poly (ethylene terephthalate) diacid and the polyethylene lactone, so that the groups of the polymer can be modified, the water-absorbing groups are introduced, and the biodegradation rate of the color master batch is improved.
In summary, the present application has the following beneficial effects:
1. polylactic acid, poly (butyl terephthalate glycol) and polymethyl ethylene carbonate can be completely biodegraded, meanwhile, the degradation time of the bio-based filler is short, the cross-linked structure of a polymer can be broken down, the poly (butyl terephthalate glycol) improves the toughness and hardness of the color master batch, and the polymethyl ethylene carbonate has an isolation effect on water and oxygen, so that the waterproof performance of the color master batch product can be improved.
2. The polyethylene glycol has hydrophilic and lipophilic properties, can be used for modifying poly (butyl terephthalate) oxalate and poly (methyl ethylene carbonate), introduces water-absorbing groups, improves biocompatibility, and active enzyme can permeate active sites of polymer macromolecules to hydrolyze, so that molecular frameworks are broken and decomposed into micromolecular products, and the degradation efficiency of the poly (butyl terephthalate) oxalate and the poly (methyl ethylene carbonate) is improved.
3. The starch is modified by utilizing dodecanoic acid chloride, and fatty acid ester groups are introduced, so that the hydrophilic and oleophobic properties of the starch are changed into the hydrophobic and oleophilic properties, the interface bonding capability of the starch and the polymer is enhanced, the degradation time of the starch is short, the cross-linked structure of the polymer can be broken, and the color master batch product can be rapidly degraded after being buried in soil.
Detailed Description
The present application will be described in further detail with reference to examples.
TABLE 1 sources and types of raw materials in preparations, examples and comparative examples
Preparation example
Preparation example 1
A modified starch is prepared by the following steps: dissolving 32kg of starch in 200kg of absolute ethyl alcohol, adding 15kg of dodecanoyl chloride, mixing and stirring uniformly, reacting for 5 hours at the temperature of 105 ℃, cooling, filtering and drying to obtain the modified starch.
Preparation example 2
A modified starch is prepared by the following steps: dissolving 45kg of starch in 250kg of absolute ethyl alcohol, adding 17kg of dodecanoyl chloride, mixing and stirring uniformly, reacting for 3 hours at the temperature of 115 ℃, cooling, filtering and drying to obtain the modified starch.
Preparation example 3
A modified starch is prepared by the following steps: dissolving 40kg of starch in 200kg of absolute ethyl alcohol, adding 11kg of dodecanoyl chloride, mixing and stirring uniformly, reacting for 4 hours at the temperature of 110 ℃, cooling, filtering and drying to obtain the modified starch.
Examples
Examples 1 to 3
A plastic color master batch capable of being efficiently biodegraded is prepared by the following steps:
s1, weighing polylactic acid, polymethyl ethylene carbonate, poly (ethylene terephthalate) and poly (ethylene lactone) in the formula, putting the materials into mixing equipment, heating the materials to the temperature shown in the table 2, and referring to the table 2 for stirring time to obtain a primary mixed material;
s2, sequentially adding the toner, the bio-based filler, the silane coupling agent and the dispersing agent into the primary blend, and stirring for a time according to a table 2 to obtain an intermediate blend;
s3, putting the intermediate mixture into an extrusion device, setting the temperature according to the table 2, setting the constant-temperature melting time according to the table 2, and then extruding, cooling and forming.
TABLE 2 summary of the components, contents and processing parameters of examples 1-3
Example 4
A plastic color masterbatch capable of being biodegraded with high efficiency, which is different from the embodiment 3 in that 8kg of polyethylene glycol is added in step S1, and the polyethylene glycol, polylactic acid, polymethyl ethylene carbonate, polybutylene terephthalate oxalate and polyethylene lactone are added into a mixing device at the same time for mixing.
Example 5
A plastic color masterbatch capable of being biodegraded with high efficiency, which is different from the plastic color masterbatch in the embodiment 3 in that in the step S1, 13kg of polyethylene glycol is added, and the polyethylene glycol, polylactic acid, polymethyl ethylene carbonate, polybutylene terephthalate oxalate and polyethylene lactone are added into a mixing device at the same time for mixing.
Example 6
A plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that starch is modified starch, and the modified starch is the modified starch obtained in preparation example 1.
Example 7
A plastic color master batch capable of being efficiently biodegraded is different from that in example 3 in that starch is modified starch, and the modified starch is the modified starch obtained in preparation example 2.
Example 8
A plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that starch is modified starch, and the modified starch is the modified starch obtained in preparation example 3.
Example 9
A plastic color masterbatch capable of being biodegraded with high efficiency, which is different from the embodiment 3 in that 13kg of polyethylene glycol is added in the step S1, and the polyethylene glycol, polylactic acid, polymethyl ethylene carbonate, polybutylene terephthalate oxalate and polyethylene lactone are added into a mixing device at the same time for mixing; the starch was modified starch obtained in preparation example 3.
Example 10
A highly efficient biodegradable plastic color masterbatch is different from the plastic color masterbatch obtained in example 3 in that the weight of polylactic acid is 50kg, the weight of poly (methyl ethylene carbonate) is 30kg, and the weight of poly (butyl terephthalate) oxalate is 25 kg.
Example 11
A highly efficient biodegradable plastic color masterbatch is different from the plastic color masterbatch obtained in example 3 in that the weight of polylactic acid is 55kg, the weight of polymethyl ethylene carbonate is 33kg, and the weight of polybutylene terephthalate is 27.5 kg.
Example 12
A highly efficient biodegradable plastic color masterbatch is different from the plastic color masterbatch obtained in example 3 in that the weight of polylactic acid is 45kg, the weight of poly (methyl ethylene carbonate) is 27kg, and the weight of poly (butyl terephthalate) is 22.5 kg.
Example 13
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the dispersing agent is prepared by mixing sodium pyrophosphate, carboxymethyl cellulose and sodium alginate according to the mass ratio of 3:2: 2.
Example 14
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the dispersing agent is prepared by mixing sodium pyrophosphate, carboxymethyl cellulose and sodium alginate according to the mass ratio of 1:3: 3.
Example 15
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the dispersing agent is prepared by mixing sodium pyrophosphate, carboxymethyl cellulose and sodium alginate according to the mass ratio of 2:1: 3.
Example 16
A plastic color master batch capable of being efficiently biodegraded is prepared by the following steps:
s1, weighing 45kg of polylactic acid, 27kg of polymethyl ethylene carbonate, 22.5kg of poly (ethylene terephthalate) and 7kg of polyethylene lactone into mixing equipment, heating to 190 ℃, and reacting for 45min under stirring to obtain a primary mixed material;
s2, sequentially adding 35kg of organic toner, 18kg of modified starch obtained in preparation example 3, 3.5kg of methacryloxy silane and 5kg of dispersing agent into the primary mixture, and stirring for 15min to obtain an intermediate mixture;
and S3, placing the intermediate blend into an extrusion device, setting the temperature to be 1300 ℃, melting for 30min at constant temperature, and then extruding, cooling and forming.
Comparative example
Comparative example 1
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the polymethyl ethylene carbonate in the raw material components is replaced by polylactic acid.
Comparative example 2
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the polybutylene terephthalate oxalate in the raw material components is replaced by polylactic acid.
Comparative example 3
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the polylactone in the raw material components is replaced by polylactic acid.
Comparative example 4
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the polymethyl ethylene carbonate and the poly (ethylene terephthalate) in the raw material components are replaced by polylactic acid.
Comparative example 5
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in the embodiment 3 in that the polyethylene lactone, the polymethyl ethylene carbonate and the polyethylene terephthalate in the raw material components are all replaced by polylactic acid.
Comparative example 6
The plastic color master batch capable of being efficiently biodegraded is different from the plastic color master batch in example 3 in that the starch in the raw material components is replaced by polylactic acid.
Performance test
And (3) measuring the tensile strength: the tensile strength (MPa) of the samples in examples 1 to 16 and comparative examples 1 to 6 was measured by a DY235 type universal material testing machine in accordance with GB/T1040 "measurement of tensile Properties of plastics";
and (3) hardness measurement: the samples of examples 1-16 and comparative examples 1-6 were measured for microhardness (MPa) using an MH25 microhardness tester, with a load of 3N, a loading rate of 0.06nm/s, and a retention time of 5 s;
the biodegradation rate is as follows: the biodegradation rate (%) of the sample 90d in examples 1 to 16 and comparative examples 1 to 6 was measured by GB/T20197-2006 "definition, Classification, identification and degradation Property requirements for degradable plastics".
TABLE 3 summary of test data for examples 1-3 and comparative examples 1-6
| Detecting items | Tensile Strength (MPa) | Hardness (MPa) | Biodegradation Rate (%) |
| Example 1 | 38.9 | 10.6 | 89.2 |
| Example 2 | 39.1 | 10.8 | 91.5 |
| Example 3 | 39.6 | 11.5 | 92.2 |
| Comparative example 1 | 39.4 | 11.0 | 87.8 |
| Comparative example 2 | 25.3 | 7.6 | 87.2 |
| Comparative example 3 | 32.4 | 8.3 | 88.3 |
| Comparative example 4 | 25.1 | 7.0 | 86.2 |
| Comparative example 5 | 24.2 | 7.0 | 86.1 |
| Comparative example 6 | 39.2 | 11.2 | 86.9 |
According to the comparison of the detection data of example 3 and comparative example 1 in table 3, the polylactic acid, the polybutylene terephthalate oxalate and the polymethyl ethylene carbonate all contain a large amount of ester bonds and can be completely biodegraded, wherein the data comparison shows that the polymethyl ethylene carbonate can improve the biodegradation rate, the hardness and the tensile strength of the color masterbatch, and the applicant speculates that the polymethyl ethylene carbonate has a synergistic effect on the tensile and high toughness performance of the polybutylene terephthalate, so that the overall mechanical performance of the color masterbatch is improved.
According to the comparison of the detection data of example 3 and comparative example 2 in table 3, it can be known that, the polybutylene terephthalate oxalate is used as the carrier of the color master batch, which contains flexible aliphatic chains and rigid aromatic chains, and the intermolecular crosslinking is tight, so that the defects of high brittleness and low hardness caused by polylactic acid can be overcome, and the hardness and tensile strength of the color master batch product can be obviously improved.
According to comparison of the detection data of the example 3 and the comparative example 3 in the table 3, the overall mechanical property of the color master batch is improved by adding the polyethylene lactone, and the inventor speculates that the interface tension of the polyethylene lactone is reduced, and the interaction of chain segments of the polylactic acid, the polybutylene terephthalate oxalate and the polymethyl ethylene carbonate is increased, so that the compatibility of the polylactic acid, the polybutylene terephthalate oxalate and the polymethyl ethylene carbonate is increased, the molecular chains are intersected to form a grid shape, and the hardness and the tensile strength of the color master batch are improved.
According to comparison of detection data of example 3 and comparative examples 1-6 in table 3, it can be seen that the defects of poor brittleness and toughness of the color master batch caused by polylactic acid can be overcome by adopting a mode of blending and combining polylactic acid, polybutylene terephthalate glycol and polymethyl ethylene carbonate, the problem of poor compatibility exists due to large interfacial tension of polylactic acid, polybutylene terephthalate glycol and polymethyl ethylene carbonate, and the biodegradation rate and comprehensive mechanical properties of the color master batch are integrally improved by increasing the compatibility of the polylactic acid, polybutylene terephthalate glycol and polymethyl ethylene carbonate and the synergistic effect of the polylactic acid, polybutylene terephthalate glycol and polymethyl ethylene carbonate.
TABLE 4 summary of test data for examples 3-9
| Detecting items | Tensile Strength (MPa) | Hardness (MPa) | Biodegradation Rate (%) |
| Example 3 | 39.6 | 11.5 | 92.2 |
| Example 4 | 39.8 | 11.8 | 94.1 |
| Example 5 | 39.8 | 12.1 | 94.6 |
| Example 6 | 39.6 | 11.7 | 93.8 |
| Example 7 | 39.7 | 11.5 | 94.2 |
| Example 8 | 39.7 | 11.9 | 94.3 |
| Example 9 | 39.9 | 12.1 | 95.4 |
According to the comparison of the test data of the examples 3 to 5 in the table 4, the polyethylene glycol has hydrophilic and lipophilic properties, and can be used for modifying the poly (butyl terephthalate) adipate and the poly (methyl ethylene carbonate), the water-absorbing groups are introduced on the functional groups of the poly (butyl terephthalate) adipate and the poly (methyl ethylene carbonate), so that the biocompatibility of the polymer is improved, the active enzyme can penetrate into the active positions of the macromolecules of the polymer to be hydrolyzed, the molecular skeleton is broken and decomposed into small molecular products, and the biodegradation rate of the color master batch is improved.
According to the comparison of the test data of the examples 3 and 6-8 in the table 4, the modified starch is used as the filler of the color master batch, the starch is modified by utilizing dodecanoic acid chloride, and the fatty acid ester group is introduced, so that the hydrophilic and oleophobic properties of the starch are changed into the hydrophobic and oleophilic properties, the interface binding capacity of the modified starch and the polymer is enhanced, the degradation time of the starch is short, the cross-linked structure of the polymer can be collapsed, the color master batch product can be rapidly degraded after being buried in soil, and the biodegradation rate of the color master batch is improved.
TABLE 5 summary of test data for examples 3, 10-12
| Detecting items | Tensile Strength (MPa) | Hardness (MPa) | Biodegradation Rate (%) |
| Example 3 | 39.6 | 11.5 | 92.2 |
| Example 10 | 41.2 | 12.1 | 92.5 |
| Example 11 | 41.8 | 12.7 | 92.3 |
| Example 12 | 42.2 | 12.9 | 92.8 |
As shown by comparing the test data of examples 3 and 10-12 in Table 5, when the ratio of polylactic acid, polybutylene terephthalate oxalate and polymethyl ethylene carbonate is limited to the range of 10:6:5, the synergistic effect of the polylactic acid, the polybutylene terephthalate and the polymethyl ethylene carbonate can improve the hardness and the tensile strength of the color master batch.
TABLE 6 summary of test data for examples 3, 13-16
| Detecting items | Tensile strength(MPa) | Hardness (MPa) | Biodegradation Rate (%) |
| Example 3 | 39.6 | 11.5 | 92.2 |
| Example 13 | 39.4 | 11.5 | 92.2 |
| Example 14 | 39.2 | 11.2 | 91.4 |
| Example 15 | 41.2 | 11.8 | 93.8 |
| Example 16 | 43.8 | 13.4 | 96.7 |
According to the comparison of the test data of the examples 3 and 13 to 16 in the table 6, the mass ratio of sodium pyrophosphate to carboxymethyl cellulose to sodium alginate is 2:1:3, so that the dispersity of the starch in the color master batch can be integrally improved, the molecular components of each part in the color master batch can be uniformly mixed, the starch can be accelerated to break down the cross-linked structure of the polymer resin, and the biodegradation rate of the color master batch can be improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The plastic color master batch capable of being efficiently biodegraded is characterized by comprising the following raw materials in parts by weight:
polylactic acid: 43-58 parts;
polymethyl ethylene carbonate: 25-35 parts;
poly (ethylene terephthalate): 22-28 parts;
polyethylene lactone: 2-7 parts;
toner: 20-42 parts;
bio-based filler: 15-18 parts;
silane coupling agent: 2.5-4.5 parts;
dispersing agent: 3-6 parts.
2. The highly efficient biodegradable plastic color masterbatch according to claim 1, wherein: the raw material components also comprise polyethylene glycol, and the weight portion of the polyethylene glycol is 8-13 portions.
3. A highly efficient biodegradable plastic masterbatch according to claim 1 or 2, characterized in that: the bio-based material is modified starch, and the preparation method of the modified starch comprises the following steps: dissolving 32-45 parts of starch in 200-250 parts of absolute ethyl alcohol, adding 11-17 parts of dodecanoic acid chloride, mixing, stirring uniformly, reacting at 105-115 ℃ for 3-5 h, cooling, filtering, and drying to obtain the modified starch.
4. The highly efficient biodegradable plastic color masterbatch according to claim 1, wherein: the mass ratio of the polylactic acid to the poly (methyl ethylene carbonate) to the poly (ethylene terephthalate) is 10:6: 5.
5. The highly efficient biodegradable plastic color masterbatch according to claim 1, wherein: the silane coupling agent is one or a combination of vinyl silane, amino silane and methacryloxy silane.
6. The highly efficient biodegradable plastic color masterbatch according to claim 1, wherein: the dispersing agent is prepared by mixing sodium pyrophosphate, carboxymethyl cellulose and sodium alginate according to the mass ratio of 2:1: 3.
7. The highly efficient biodegradable plastic color masterbatch according to claim 1, wherein: the toner is organic toner.
8. A method for preparing a highly efficient biodegradable plastic masterbatch, based on the highly efficient biodegradable plastic masterbatch of any one of claims 1-7, comprising the following steps:
s1, weighing polylactic acid, polymethyl ethylene carbonate, poly (ethylene terephthalate) and polyethylene lactone in the formula, putting the materials into mixing equipment, heating the materials to the temperature of 180-205 ℃, and reacting the materials for 40-55 min under stirring to obtain a primary mixed material;
s2, sequentially adding the toner, the bio-based filler, the silane coupling agent and the dispersing agent into the primary mixed material, and stirring for 15-20 min to obtain an intermediate mixed material;
s3, placing the intermediate mixture into an extrusion device, setting the temperature to be 120-140 ℃, melting at constant temperature for 30-40 min, and then extruding, cooling and forming.
9. The highly efficient biodegradable plastic color masterbatch according to claim 8, wherein: in the step S1, the preliminary mixture further includes polyethylene glycol, and the polyethylene glycol and the polylactic acid, the polymethyl ethylene carbonate, the polybutylene terephthalate oxalate and the polyethylene lactone are simultaneously added to a mixing device to be mixed.
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