CN117603522A - Full-biodegradation plastic master batch and preparation method and application thereof - Google Patents

Full-biodegradation plastic master batch and preparation method and application thereof Download PDF

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Publication number
CN117603522A
CN117603522A CN202410089312.8A CN202410089312A CN117603522A CN 117603522 A CN117603522 A CN 117603522A CN 202410089312 A CN202410089312 A CN 202410089312A CN 117603522 A CN117603522 A CN 117603522A
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parts
full
master batch
succinic anhydride
plastic master
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CN117603522B (en
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谢学文
戴长松
常耀辉
郑海勇
程远方
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Sichuan Tengdafeng Rubber Technology Co ltd
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Sichuan Tengdafeng Rubber Technology Co ltd
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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
    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Abstract

The invention relates to the technical field of plastics, and provides a full-biodegradation plastic master batch, a preparation method and application thereof. The full-biodegradation plastic master batch comprises the following raw materials in parts by mass: 10-20 parts of polyolefin resin, 80-90 parts of heavy calcium carbonate, 0.1-0.5 part of lignocellulose, 1-3 parts of chitosan, 3-5 parts of stearate, 1-3 parts of lubricant, 1-2 parts of antioxidant and 5-10 parts of benzyl succinic anhydride. By the technical scheme, the problems of low material strength caused by low compatibility and poor interface adhesion between calcium carbonate and polyolefin resin in the prior art are solved.

Description

Full-biodegradation plastic master batch and preparation method and application thereof
Technical Field
The invention relates to the technical field of plastics, in particular to a full-biodegradable plastic master batch, a preparation method and application thereof.
Background
The degradable plastic is a product which is developed greatly for eliminating white pollution at home and abroad, and varieties such as biodegradable plastic, photodegradable plastic, photo-biodegradable plastic and the like have been developed in China. Biodegradable plastics are divided into two types, one is a fully biodegradable plastic, such as: polymers synthesized by microorganisms, natural polymers and derivatives thereof, synthetic aliphatic polyesters, polyethylene glycol, polyvinyl alcohol and the like; the other is partially biodegradable plastic, of which the most representative is starch filled resin. From the trend of development, low-cost fully biodegradable plastics are a powerful development direction of degradable plastics.
At present, the full-biodegradable plastic material comprises matrix resin, filler and auxiliary agent, wherein the filler is also called filler, and refers to solid fine materials which can improve the processing performance of the material, the mechanical property of the product and/or reduce the cost. The calcium carbonate is the most widely used inorganic powdery filler in the plastic industry at present, and is divided into light calcium carbonate, heavy calcium carbonate, colloid calcium carbonate and amorphous calcium carbonate, wherein the heavy calcium carbonate is prepared by mineral separation, crushing, grading and surface treatment of limestone, is colorless and odorless white powder, is almost insoluble in water and is most widely used. However, polyolefin resins are rarely used, and because polyolefin is nonpolar and has hydrophobicity, compatibility with calcium carbonate having strong hydrophilicity is small, and because polyolefin is crystalline resin, volume is reduced when cooled after melting, adhesion to inorganic calcium carbonate interface is poor, resulting in further improvement of strength of material.
Disclosure of Invention
The invention provides a full-biodegradation plastic master batch, a preparation method and application thereof, and solves the problems of low material strength caused by low compatibility and poor interface adhesion between calcium carbonate and polyolefin resin in the related technology.
The technical scheme of the invention is as follows:
the full-biodegradation plastic master batch comprises the following raw materials in parts by mass: 10-20 parts of polyolefin resin, 80-90 parts of heavy calcium carbonate, 0.1-0.5 part of lignocellulose, 1-3 parts of chitosan, 3-5 parts of stearate, 1-3 parts of lubricant, 1-2 parts of antioxidant and 5-10 parts of benzyl succinic anhydride.
As a further technical scheme, the method also comprises alkyl succinic anhydride.
As a further technical scheme, the mass ratio of the benzyl succinic anhydride to the alkyl succinic anhydride is 8:3-5.
As a further technical scheme, the number of carbon atoms of the alkyl in the alkyl succinic anhydride is more than or equal to 6.
As a further technical scheme, the number of carbon atoms of the alkyl in the alkyl succinic anhydride is less than or equal to 10.
As a further technical scheme, the alkyl succinic anhydride is n-octyl succinic anhydride.
As a further technical scheme, the polyolefin resin comprises one or two of polyethylene resin and polypropylene resin;
the stearate comprises one or more of magnesium stearate, zinc stearate and barium stearate;
the lubricant comprises one or two of polyethylene wax and stearic acid;
the antioxidant comprises one or more of antioxidant 168, antioxidant 1010 and antioxidant 1076.
The invention also provides a preparation method of the full-biodegradation plastic master batch, which comprises the following steps: and (3) mixing the raw materials uniformly, banburying and extruding to obtain the full-biodegradation plastic master batch.
As a further technical scheme, the temperature during mixing is 80-100 ℃ and the time is 5-12 min.
The invention also provides application of the full-biodegradable plastic master batch or the full-biodegradable plastic master batch prepared by the preparation method in a film.
The working principle and the beneficial effects of the invention are as follows:
1. the invention provides a full-biological degradable plastic master batch, wherein chitosan can be used as a carrier of microorganisms in soil during degradation, which is beneficial to mass propagation of the microorganisms, thereby realizing better degradation effect. In addition, the invention takes the heavy calcium carbonate as the filler, reduces the resin content and the cost, simultaneously adds the benzyl succinic anhydride to improve the hydrophilicity of the heavy calcium carbonate, improves the dispersion stability of the heavy calcium carbonate in the polyolefin resin, and improves the adhesion of the interface between the polyolefin resin and the heavy calcium carbonate, thereby improving the tensile strength and the impact strength of the full-biodegradable plastic master batch.
2. According to the invention, alkyl succinic anhydride is added on the basis of benzyl succinic anhydride, so that the tensile strength and impact strength of the full-biodegradable plastic master batch are further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The polyethylene resin in the following examples and comparative examples was polyethylene resin HD5502GA; the polypropylene resin is polypropylene resin J340; the mesh number of the heavy calcium carbonate is 800 meshes, and the content of the calcium carbonate is 98.5 weight percent; the degree of deacetylation of chitosan was 85%.
Example 1
85 parts of heavy calcium carbonate and 8 parts of benzyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, added with 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant, and uniformly mixed, then transferred into an internal mixer, banburying for 20 minutes at 150 ℃ and 720r/min, transferred into an extruder, extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 2
Adding 80 parts of heavy calcium carbonate and 5 parts of benzyl succinic anhydride into a mixer, mixing for 12min at 80 ℃, adding 10 parts of polypropylene resin, 0.1 part of lignocellulose, 1 part of chitosan, 3 parts of barium stearate, 1 part of stearic acid and 1010 1 parts of antioxidant, uniformly mixing, transferring to an internal mixer, banburying for 15min at 150 ℃ at 720r/min, transferring to an extruder, extruding at 650r/min, and obtaining the full-biodegradation plastic master batch.
Example 3
90 parts of heavy calcium carbonate and 10 parts of benzyl succinic anhydride are added into a mixer, mixed for 5min at 100 ℃, added with 20 parts of polypropylene resin, 0.5 part of lignocellulose, 3 parts of chitosan, 5 parts of magnesium stearate, 3 parts of polyethylene wax and 1076 parts of antioxidant, and after being uniformly mixed, the mixture is transferred into an internal mixer, banburying for 25min at 150 ℃ and 720r/min, transferred into an extruder and extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 4
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 1 part of butyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, added with 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant, and uniformly mixed, then transferred into an internal mixer, banburying for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 5
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 3 parts of butyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, added with 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant, and uniformly mixed, then transferred into an internal mixer, banburying for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 6
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 5 parts of butyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, added with 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant, and uniformly mixed, then transferred into an internal mixer, banburying for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 7
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 7 parts of butyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, added with 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant, and uniformly mixed, then transferred into an internal mixer, banburying for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 8
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 5 parts of hexyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant are added, and after being uniformly mixed, the mixture is transferred into an internal mixer, banburying is carried out for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, and extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 9
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 5 parts of n-octyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant are added, and after being uniformly mixed, the mixture is transferred into an internal mixer, banburying is carried out for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, and extruded at 650r/min, thus obtaining the full-biodegradation plastic master batch.
Example 10
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 5 parts of decyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant are added, and after being uniformly mixed, the mixture is transferred into an internal mixer, banburying is carried out for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, and extruded at 650r/min to obtain the full-biodegradation plastic master batch.
Example 11
85 parts of heavy calcium carbonate, 8 parts of benzyl succinic anhydride and 5 parts of dodecyl succinic anhydride are added into a mixer, mixed for 8 minutes at 90 ℃, added with 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 168.5 parts of antioxidant, and uniformly mixed, then transferred into an internal mixer, banburying for 20 minutes at 150 ℃ at 720r/min, transferred into an extruder, extruded at 650r/min, and finally the full-biodegradation plastic master batch is obtained.
Comparative example 1
85 parts of heavy calcium carbonate, 15 parts of polyethylene resin, 0.3 part of lignocellulose, 2 parts of chitosan, 4 parts of zinc stearate, 2 parts of polyethylene wax and 1.5 parts of antioxidant are uniformly mixed, and then are transferred to an internal mixer to be internally mixed for 20min at 150 ℃ at 720r/min, are transferred to an extruder, and are extruded at the rotating speed of 650r/min, so that the full-biodegradation plastic master batch is obtained.
50 parts of the total biodegradable plastic master batches obtained in examples 1-11 and comparative example 1 and 50 parts of polyethylene resin were respectively mixed and blow-molded at 120 ℃ to obtain degradable films.
Performance test:
the degradable films obtained in examples 1 to 11 and comparative example 1 were respectively referred to GB/T1040.3-2006, determination of Plastic tensile Property part 3: test conditions for films and sheets the method in "test conditions for tensile strength, sample type: type 4 sample, test speed 50mm/min; determination of impact Properties of Plastic simply-supported Beam section 1, reference GB/T1043.1-2008: the method in the non-instrumented impact test performs the test of the unnotched impact strength, and the thickness of a sample is 4mm; the test results are recorded in table 1.
TABLE 1 tensile Strength and unnotched impact Strength
As can be seen from Table 1, the tensile strength of the degradable film prepared from the full-biodegradable plastic master batch provided by the invention is more than 23.5MPa, and the impact strength without gaps is 6.0kJ/m 2 The above.
Compared with comparative example 1, examples 1-11 are prepared by adding benzyl succinic anhydride in examples 1-11, and comparative example 1 is prepared without adding benzyl succinic anhydride, and the tensile strength and the unnotched impact strength of the degradable film obtained in examples 1-11 are higher than those of comparative example 1, which shows that the tensile strength and the impact strength of the full-biodegradation plastic master batch can be improved by adding benzyl succinic anhydride, so that the tensile strength and the impact strength of the degradable film are improved.
Examples 4 to 11 compared with example 1, the addition of alkyl succinic anhydride in examples 4 to 11, and no alkyl succinic anhydride in example 1, the tensile strength and the unnotched impact strength of the degradable film obtained in examples 4 to 11 are higher than those of example 1, which means that the addition of alkyl succinic anhydride on the basis of benzyl succinic anhydride can further improve the tensile strength and the impact strength of the fully biodegradable plastic master batch, thereby further improving the tensile strength and the impact strength of the degradable film.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The full-biodegradation plastic master batch is characterized by comprising the following raw materials in parts by mass: 10-20 parts of polyolefin resin, 80-90 parts of heavy calcium carbonate, 0.1-0.5 part of lignocellulose, 1-3 parts of chitosan, 3-5 parts of stearate, 1-3 parts of lubricant, 1-2 parts of antioxidant and 5-10 parts of benzyl succinic anhydride.
2. A fully biodegradable plastic masterbatch according to claim 1, characterized in that it further comprises alkyl succinic anhydrides.
3. The full-biodegradable plastic master batch according to claim 2, wherein the mass ratio of the benzyl succinic anhydride to the alkyl succinic anhydride is 8:3-5.
4. A full biodegradable plastic masterbatch according to claim 3, characterized in that the alkyl group of said alkyl succinic anhydride has a number of carbon atoms not less than 6.
5. The full-biodegradable plastic master batch according to claim 4, wherein the alkyl group of the alkyl succinic anhydride has a carbon number of 10 or less.
6. A fully biodegradable plastic masterbatch according to claim 5, characterized in that said alkyl succinic anhydride is n-octyl succinic anhydride.
7. The full biodegradable plastic masterbatch according to claim 1, characterized in that said polyolefin resin comprises one or both of polyethylene resin and polypropylene resin.
8. The full biodegradable plastic masterbatch according to claim 1, characterized in that said stearate comprises one or more of magnesium stearate, zinc stearate, barium stearate;
the lubricant comprises one or two of polyethylene wax and stearic acid;
the antioxidant comprises one or more of antioxidant 168, antioxidant 1010 and antioxidant 1076.
9. The preparation method of the full-biodegradable plastic master batch according to any one of claims 1 to 8, which is characterized by comprising the following steps: and (3) mixing the raw materials uniformly, banburying and extruding to obtain the full-biodegradation plastic master batch.
10. The use of the all-biodegradable plastic master batch according to any one of claims 1 to 8 or the all-biodegradable plastic master batch prepared by the preparation method of claim 9 in a film.
CN202410089312.8A 2024-01-23 2024-01-23 Full-biodegradation plastic master batch and preparation method and application thereof Active CN117603522B (en)

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