CN117362798A - Preparation method of degradable plastic mixed particles - Google Patents
Preparation method of degradable plastic mixed particles Download PDFInfo
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- CN117362798A CN117362798A CN202311330476.7A CN202311330476A CN117362798A CN 117362798 A CN117362798 A CN 117362798A CN 202311330476 A CN202311330476 A CN 202311330476A CN 117362798 A CN117362798 A CN 117362798A
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- degradable plastic
- mixed particles
- plastic mixed
- inorganic salt
- pure water
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- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 50
- 239000002245 particle Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000010008 shearing Methods 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 36
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical class [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000011282 treatment Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 24
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 24
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 22
- 229920000945 Amylopectin Polymers 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 20
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 13
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011246 composite particle Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004373 Pullulan Substances 0.000 claims description 2
- 229920001218 Pullulan Polymers 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 235000019423 pullulan Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 32
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000011269 treatment regimen Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/12—Amylose; Amylopectin; Degradation products 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a preparation method of degradable plastic mixed particles, which comprises the steps of gelatinizing amylopectin, and then adding a plasticizer to prepare thermoplastic starch slurry; preparing modified inorganic salt whisker slurry by using a coupling agent, pure water and inorganic salt whiskers; mixing thermoplastic starch slurry, modified calcium sulfate whisker slurry and composite antioxidant, adding polyethylene resin and polyamide resin, and performing microwave treatment in a high-speed shearing process; and extruding, granulating and drying to obtain the degradable plastic mixed particles. The preparation method of the degradable plastic mixed particles can enable the degradable plastic mixed particles to have higher mechanical property and good degradation property.
Description
Technical Field
The invention relates to a preparation method of degradable plastic mixed particles, and belongs to the technical field of degradable plastics.
Background
Plastic products have been widely used in people's daily lives. The traditional general plastic for olefin, such as polyethylene, polypropylene, polystyrene and the like, is difficult to degrade in the natural environment and causes serious pollution to the human environment.
In order to solve the pollution problem of the traditional plastics, the national development planning and industrial policy are complied, and some general-purpose olefin plastics are mixed with biodegradable substances, such as starch and polyolefin, so that the materials lose mechanical properties and shape, partial degradation can occur in natural environment, the same effect as the biodegradability can be produced through composting, and other biodegradable plastics are prepared by taking aliphatic polyester, polyvinyl alcohol, polyethylene glycol and the like as raw materials, or biological bases such as industrial starch, plant fiber, polyamino glucose and the like as raw materials, but compared with the traditional plastics, the mechanical properties of the biodegradable plastics are poorer.
Disclosure of Invention
At least aiming at the problems in the prior art, the invention provides a preparation method of degradable plastic mixed particles, which can have higher mechanical property and good degradation property.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for preparing degradable plastic mixed particles, which comprises the following steps:
(1) Mixing amylopectin and pure water uniformly, heating for gelatinization, adding a plasticizer, heating to 110-115 ℃, and shearing at high speed to obtain thermoplastic starch slurry;
(2) Uniformly mixing a coupling agent and pure water, adding inorganic salt whiskers, heating to 90-95 ℃, and shearing at high speed to obtain modified inorganic salt whisker slurry, wherein the quality of the pure water in the step (1) is twice that of the pure water in the step (2);
(3) Firstly, uniformly mixing thermoplastic starch slurry, modified calcium sulfate whisker slurry and a composite antioxidant, then adding polyethylene resin and polyamide resin at 120-125 ℃, and then carrying out microwave treatment in a high-speed shearing process to obtain a mixed material;
(4) And (3) delivering the mixed material into a double-screw extruder for extrusion granulation and drying to obtain the degradable plastic mixed particles.
Preferably, the polyethylene resin, the polyamide resin, the pullulan, the inorganic salt whisker, the plasticizer, the coupling agent, the compound antioxidant and the pure water are calculated according to mass percent: 25 to 28 percent of polyethylene resin, 21 to 23.5 percent of polyamide resin, 16 to 18 percent of amylopectin, 7 to 10 percent of plasticizer, 3.7 to 4.2 percent of inorganic salt whisker, 2.2 to 2.7 percent of coupling agent, 0.3 to 0.4 percent of compound antioxidant and the balance of pure water.
Preferably, the plasticizer is polyethylene glycol or acetyl tributyl citrate.
Preferably, the inorganic salt whisker is a calcium sulfate whisker or a basic magnesium sulfate whisker.
Preferably, the coupling agent is one of silane coupling agent K-450, titanate coupling agent HY311W or maleic anhydride.
Preferably, the composite oxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 3:1.
Preferably, in the step (1), the gelatinization temperature is 85-90 ℃ and the gelatinization time is 25-30 min.
Preferably, in the step (1), the time of high-speed shearing is 80-90 min.
Preferably, in the step (2), the time of high-speed shearing is 120-150 min.
Preferably, in the step (3), the high-speed shearing time is 90-120 min, and the microwave treatment is carried out every 10-15 min in the high-speed shearing process, the time of each microwave treatment is 2-3 min, and the microwave power is 20-25 KHz.
Preferably, in step (4), the extrusion conditions are: the extrusion temperature is 170-180 ℃, and the extrusion pressure is 85-90 MPa.
The invention has the beneficial effects that: the preparation method of the degradable plastic mixed particles is simple and easy to implement, has strong operability and good processing performance; according to the preparation method of the degradable plastic mixed particles, the combined components are combined with microwave treatment in the high-speed shearing process, and the obtained degradable plastic mixed particles have high mechanical properties and good degradation properties; according to the invention, the amylopectin is modified into thermoplastic amylopectin, and the thermoplastic amylopectin is cooperated with polyethylene resin and polyamide resin raw materials, so that the degradable plastic mixed particles have good degradability while the mechanical properties such as tensile strength, bending strength, impact strength and the like of the degradable plastic mixed particles are improved; in addition, the inorganic salt whisker is modified and better combined with the raw materials of polyethylene resin and polyamide resin, so that the mechanical property of the degradable plastic mixed particles is further improved.
Detailed Description
The invention will now be more clearly and more fully described by way of the following specific examples, which are not intended to be limiting.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents, instruments and components used are conventional products commercially available without identifying the manufacturer.
Example 1
A preparation method of degradable plastic mixed particles comprises the following specific steps:
(1) Mixing 160g of amylopectin and 150g of pure water uniformly at 350rpm, heating to 85-90 ℃ for gelatinization for 25min, adding 70g of acetyl tributyl citrate, heating to 110-115 ℃, and shearing at 2200rpm for 90min to obtain thermoplastic starch slurry;
(2) Uniformly mixing 22g of a silane coupling agent K-450 and 75g of pure water at 350rpm, adding 37g of calcium sulfate whisker, heating to 90-95 ℃, and shearing at a high speed at 2200rpm for 120min to obtain modified inorganic salt whisker slurry;
(3) Firstly, uniformly mixing 3g of thermoplastic starch slurry, modified calcium sulfate whisker slurry and composite antioxidant which is formed by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 at 350rpm, adding 250g of polyethylene resin and 233g of polyamide PA resin at 120-125 ℃, and performing microwave treatment at 20KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2200rpm to obtain a mixed material;
(4) And (3) feeding the mixed material into a double-screw extruder, extruding and granulating at the extrusion temperature of 170-180 ℃ and the extrusion pressure of 85MPa, and drying to obtain the degradable plastic mixed particles.
Example 2
A preparation method of degradable plastic mixed particles comprises the following specific steps:
(1) 180g of amylopectin and 120g of pure water are uniformly mixed at 300rpm, heated to 85-90 ℃ for gelatinization for 30min, then 100g of polyethylene glycol is added, the temperature is raised to 110-115 ℃, and high-speed shearing is carried out for 85min at 2000rpm, thus obtaining thermoplastic starch slurry;
(2) Mixing 27g of maleic anhydride and 60g of pure water uniformly at 300rpm, adding 40g of calcium sulfate whisker, heating to 90-95 ℃, and shearing at 2000rpm for 135min to obtain modified inorganic salt whisker slurry;
(3) Firstly, uniformly mixing 3g of thermoplastic starch slurry, modified calcium sulfate whisker slurry and composite antioxidant prepared by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 at 300-400 rpm, adding 260g of polyethylene resin and 210g of polyamide PA resin at 120-125 ℃, and performing microwave treatment at 22KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2000rpm to obtain a mixed material;
(4) And (3) feeding the mixed material into a double-screw extruder, extruding and granulating at the extrusion temperature of 170-180 ℃ and the extrusion pressure of 90MPa, and drying to obtain the degradable plastic mixed particles.
Example 3
A preparation method of degradable plastic mixed particles comprises the following specific steps:
(1) Uniformly mixing 170g of amylopectin and 116g of pure water at 400rpm, heating to 85-90 ℃ for gelatinization for 28min, adding 85g of polyethylene glycol, heating to 110-115 ℃, and shearing at 2100rpm for 80min to obtain thermoplastic starch slurry;
(2) Uniformly mixing 25g of titanate coupling agent HY311W and 58g of pure water at 300-400 rpm, adding 42g of basic magnesium sulfate whisker, heating to 90-95 ℃, and shearing at 2100rpm for 150min to obtain modified inorganic salt whisker slurry;
(3) Mixing thermoplastic starch slurry, modified calcium sulfate whisker slurry, and 4g of composite antioxidant prepared by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 uniformly at 400rpm, adding 280g of polyethylene resin and 220g of polyamide PA resin at 120-125 ℃, and performing microwave treatment at 25KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2100rpm to obtain a mixed material;
(4) And (3) feeding the mixed material into a double-screw extruder, extruding and granulating at the extrusion temperature of 170-180 ℃ and the extrusion pressure of 88MPa, and drying to obtain the degradable plastic mixed particles.
Example 4
A preparation method of degradable plastic mixed particles comprises the following specific steps:
(1) Mixing 175g of amylopectin and 110g of pure water uniformly at 300rpm, heating to 85-90 ℃ for gelatinization for 30min, adding 81g of acetyl tributyl citrate, heating to 110-115 ℃, and shearing at 2000rpm for 80min to obtain thermoplastic starch slurry;
(2) Uniformly mixing 24.5g of a silane coupling agent K-450 and 55g of pure water at 300rpm, adding 41g of inorganic salt calcium sulfate whisker, heating to 90-95 ℃, and shearing at 2000rpm for 140min to obtain modified inorganic salt whisker slurry;
(3) Firstly, uniformly mixing 3.5g of thermoplastic starch slurry, modified calcium sulfate whisker slurry and composite antioxidant prepared by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 at 300rpm, adding 275g of polyethylene resin and 235g of polyamide PA resin at 120-125 ℃, and performing microwave treatment at 25KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2000rpm to obtain a mixed material;
(4) And (3) feeding the mixed material into a double-screw extruder, extruding and granulating at the extrusion temperature of 170-180 ℃ and the extrusion pressure of 90MPa, and drying to obtain the degradable plastic mixed particles.
Example 5
A preparation method of degradable plastic mixed particles comprises the following specific steps:
(1) Mixing 140g of amylopectin and 95.2g of pure water uniformly at 400rpm, heating to 85-90 ℃ for gelatinization for 30min, adding 72g of acetyl tributyl citrate, heating to 110-115 ℃, and shearing at 2100rpm for 85min to obtain thermoplastic starch slurry;
(2) Uniformly mixing 19.2g of a silane coupling agent K-450 and 47.6g of pure water at 300rpm, adding 31.2g of calcium sulfate whisker, heating to 90-95 ℃, and shearing at 2200pm for 150min at high speed to obtain modified inorganic salt whisker slurry;
(3) Firstly, uniformly mixing 2.8g of thermoplastic starch slurry, modified calcium sulfate whisker slurry and composite antioxidant formed by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 at 300rpm, then adding polyethylene resin and polyamide PA resin at 120-125 ℃, and then carrying out microwave treatment at 20KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2000rpm, wherein the time of each microwave treatment is 90min, thus obtaining a mixed material;
(4) And (3) feeding the mixed material into a double-screw extruder, extruding and granulating at the extrusion temperature of 170-180 ℃ and the extrusion pressure of 85MPa, and drying to obtain the degradable plastic mixed particles.
Example 6
A preparation method of degradable plastic mixed particles comprises the following specific steps:
(1) Mixing 198g of amylopectin and 172g of pure water uniformly at 350rpm, heating to 85-90 ℃ for gelatinization for 25min, adding 90g of polyethylene glycol, heating to 110-115 ℃, and shearing at 2000rpm for 80min to obtain thermoplastic starch slurry;
(2) Mixing 27g of maleic anhydride and 86.4g of pure water uniformly at 350rpm, adding 45.6g of calcium sulfate whisker, heating to 90-95 ℃, and shearing at 2000rpm for 120min to obtain modified inorganic salt whisker slurry;
(3) Mixing thermoplastic starch slurry, modified calcium sulfate whisker slurry, and composite antioxidant 4.2g prepared by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 uniformly at 350rpm, adding 318g of polyethylene resin and 258g of polyamide PA66 resin at 120-125 ℃, and performing microwave treatment at 20KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2000rpm to obtain a mixed material;
(4) And (3) feeding the mixed material into a double-screw extruder, extruding and granulating at the extrusion temperature of 170-180 ℃ and the extrusion pressure of 90MPa, and drying to obtain the degradable plastic mixed particles.
Comparative example 1
The preparation process was partially identical to that of example 4, except that: the treatment modes of the mixed materials obtained in the step (3) are different, in the step (3) of the comparative example 1, thermoplastic starch slurry, modified calcium sulfate whisker slurry and 3.5g of composite antioxidant formed by mixing antioxidant 1010 and antioxidant 168 according to the mass ratio of 3:1 are uniformly mixed at 300rpm, 275g of polyethylene resin and 235g of polyamide resin are added at 120-125 ℃, then high-speed shearing is carried out for 110min at 2000rpm, and microwave treatment is carried out for 20min at 25KHz, thus obtaining the mixed materials;
the remainder being identical.
Comparative example 2
The preparation process was partially identical to that of example 4, except that: amylopectin and inorganic salt whisker treatment modes are different; the treatment pattern obtained by removing step (1) and modifying the modified inorganic salt whisker slurry of step (2) in comparative example 2 was changed as follows:
(1) Uniformly mixing 24.5g of a silane coupling agent K-450, 81g of acetyl tributyl citrate and 165g of pure water at 300rpm, adding 41g of inorganic salt calcium sulfate whisker, heating to 90-95 ℃, shearing at 2000rpm for 140min, adding 175g of amylopectin, heating to 110-115 ℃ and shearing at 2000rpm for 80min to obtain modified inorganic salt whisker slurry;
(3) Firstly, uniformly mixing 3.5g of modified calcium sulfate whisker slurry and a composite antioxidant prepared by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 3:1 at 300rpm, adding 275g of polyethylene resin and 235g of polyamide PA resin at 120-125 ℃, and then carrying out microwave treatment at 25KHz for 2-3 min every 10-15 min in a high-speed shearing process at 2000rpm, wherein the time of each microwave treatment is 110min, so as to obtain a mixed material;
the remainder being identical.
Comparative example 3
The preparation process was partially identical to that of example 4, except that: starch selection, amylose is selected for step (1) in comparative example 3;
the remainder being identical.
Comparative example 4
The preparation process was partially identical to that of example 4, except that: whether the surface of the inorganic salt whisker is treated or not, the surface of the inorganic salt whisker in comparative example 3 is not treated as follows:
(1) Mixing 175g of amylopectin and 189.5g of pure water uniformly at 300rpm, heating to 85-90 ℃ for gelatinization for 30min, adding 81g of acetyl tributyl citrate, heating to 110-115 ℃, and shearing at 2000rpm for 80min to obtain thermoplastic starch slurry;
(2) Firstly, uniformly mixing 3.5g of thermoplastic starch slurry, calcium sulfate whisker, and composite antioxidant formed by mixing antioxidant 1010 and antioxidant 168 according to a mass ratio of 3:1 at 300rpm, then adding 275g of polyethylene resin and 235g of polyamide PA resin at 120-125 ℃, and then carrying out microwave treatment at 25KHz every 10-15 min in a high-speed shearing process at 2000rpm for 2-3 min, and carrying out high-speed shearing treatment for 110min to obtain a mixed material;
the remainder being identical.
Comparative example 5
The preparation process was partially identical to that of example 4, except that: whether or not inorganic salt whisker was added, the inorganic salt whisker was not added in comparative example 5, as follows:
(1) Mixing 185g of amylopectin and 176g of pure water uniformly at 300rpm, heating to 85-90 ℃ for gelatinization for 30min, adding 81g of acetyl tributyl citrate, heating to 110-115 ℃, and shearing at 2000rpm for 80min to obtain thermoplastic starch slurry;
(3) Firstly, uniformly mixing thermoplastic starch slurry, 24.5g of a silane coupling agent K-450, 3.5g of a composite antioxidant formed by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 3:1 at 300rpm, adding 285g of polyethylene resin and 245g of polyamide PA resin at 120-125 ℃, and carrying out microwave treatment at 25KHz every 10-15 min in a high-speed shearing process at 2000rpm for 2-3 min, and carrying out high-speed shearing treatment for 110min to obtain a mixed material;
the remainder being identical.
Comparative example 6
The preparation process was partially identical to that of example 4, except that: whether polyamide resin is added or not, in the step (3) in the comparative example 6, thermoplastic starch slurry, modified calcium sulfate whisker slurry and 3.5g of composite antioxidant formed by mixing antioxidant 1010 and antioxidant 168 according to the mass ratio of 3:1 are uniformly mixed at 300rpm, then after 510g of polyethylene resin is added at 120-125 ℃, microwave treatment is carried out at 25KHz every 10-15 min in the high-speed shearing process of 2000rpm, the time of each microwave treatment is 2-3 min, and the high-speed shearing treatment is 110min, thus obtaining a mixed material;
the remainder being identical.
Comparative example 7
The preparation process was partially identical to that of example 1, except that: the content of inorganic salt whisker, step (2) in comparative example 7, silane coupling agent K-450 g and pure water 76g are mixed evenly at 350rpm, 36g of calcium sulfate whisker is added, the temperature is raised to 90-95 ℃, and high-speed shearing is carried out for 120min at 2200rpm, thus obtaining modified inorganic salt whisker slurry;
the remainder being identical.
Comparative example 8
The preparation process was partially identical to that of example 3, except that: the content of inorganic salt whisker, step (2) in comparative example 8, evenly mixing titanate coupling agent HY311W 25g and pure water 57g at 300-400 rpm, adding basic magnesium sulfate whisker 43g, heating to 90-95 ℃, and shearing at 2100rpm for 150min to obtain modified inorganic salt whisker slurry;
the remainder being identical.
Effect examples
1. Mechanical property test
The degradable plastic composite particles prepared in examples 1 to 6 and comparative examples 1 to 8, the pure polyethylene of the control group 1 and the pure polyamide PA of the control group 2 were prepared into respective bars:
each sample strip 110mm long by 25mm wide by 4mm thick was tested for tensile properties according to GB/T1040-2018;
each sample strip 80mm long by 10mm wide by 4mm thick was tested according to the bending property of GB/T9341-2008;
each sample strip 80mm long by 10mm wide by 4mm thick was tested for impact strength according to GB/T1843-2008 and the test results are shown in Table 1 below.
2. The degradation performance of the soil burial is tested,
the degradable plastic mixed particles prepared in examples 1 to 6 and comparative examples 1 to 8, the pure polyethylene of the control group 1 and the pure polyamide PA of the control group 2 are prepared into sample bars with the thickness of 120mm multiplied by 1mm, and the initial mass m of the sample is recorded by drying and weighing 0 Wrapping the sample with single-layer gauze, marking with number, burying in soil with depth of about 20cm in natural environment, taking out the sample after three months, washing the surface of the sample with tap water, 75% ethanol and distilled water sequentially, oven drying, weighing, and recording mass m of the degraded sample 1 Sample degradation mass loss rate = [ (m) 0 -m 1 )/m 0 ]*100%, degradation mass loss rate test results of each sample are shown in the following table 2:
TABLE 1 mechanical Properties
| Tensile Strength (MPa) | Flexural Strength (MPa) | Impact Strength (kJ/m 2) | |
| Example 1 | 68.3 | 97.9 | 42.3 |
| Example 2 | 69.9 | 98.5 | 45.2 |
| Examples3 | 73.3 | 101.3 | 44.6 |
| Example 4 | 74.3 | 103.4 | 47.5 |
| Example 5 | 73.5 | 102.1 | 46.3 |
| Example 6 | 72.6 | 103.6 | 47.2 |
| Comparative example 1 | 63.8 | 92.1 | 26.5 |
| Comparative example 2 | 53.6 | 83.3 | 16.6 |
| Comparative example 3 | 64.4 | 94.5 | 37.6 |
| Comparative example 4 | 61.5 | 91.4 | 20.7 |
| Comparative example 5 | 52.3 | 81.3 | 18.2 |
| Comparative example 6 | 37.8 | 46.5 | 34.5 |
| Comparative example 7 | 64.3 | 93.5 | 36.5 |
| Comparative example 8 | 65.2 | 92.7 | 34.5 |
| Control group 1 | 20.1 | 22.1 | 17.4 |
| Control group 2 | 60.5 | 90.3 | 6.3 |
TABLE 2 degradation Properties
As can be seen from the above tables 1 and 2, the preparation method of the degradable plastic mixed particles of the present invention is simple and easy, and has strong operability and good processability.
Compared with the control group 1 and the control group 2, the degradable plastic mixed particles have higher mechanical property and good degradation property; compared with the comparative example 1, in the preparation process of the degradable plastic mixed particle, the combination of the components is combined with the microwave treatment in the high-speed shearing process, so that the mechanical property of the degradable plastic mixed particle can be improved, the tensile strength is improved by at least 7%, the bending strength is improved by at least 6%, and the impact strength is improved by at least 59.5%; compared with comparative examples 2 and 3, the thermoplastic amylopectin can greatly improve the combination of the polyamide resin and the polyethylene resin, and simultaneously synergistically modify the inorganic salt whisker to further improve the mechanical property of the degradable plastic mixed particles; compared with comparative examples 4 and 5, the inorganic salt whisker can improve the tensile strength, bending strength and impact strength of the degradable plastic mixed particles, and the inorganic salt whisker modified by the surface coupling agent can be combined with the plastic, so that the mechanical property of the degradable plastic mixed particles is further improved; compared with comparative example 6, the mechanical property of the degradable plastic mixed particles can be greatly improved by using the polyamide resin and the polyethylene resin, the tensile strength is improved by at least 80 percent, the bending strength is improved by at least 110 percent, and the impact strength is improved by at least 16.5 percent; too small an amount of modified inorganic salt whiskers compared to comparative example 7, comparative example 8 may cause a decrease in mechanical properties of the degradable plastic composite particles.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution of the present invention, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the present invention may be modified or equivalently replaced without departing from the spirit and scope of the present invention, and any modification or partial replacement thereof should be included in the scope of the claims of the present invention.
Claims (10)
1. A method for preparing degradable plastic mixed particles, which is characterized by comprising the following steps:
(1) Mixing amylopectin and pure water uniformly, heating for gelatinization, adding a plasticizer, heating to 110-115 ℃, and shearing at high speed to obtain thermoplastic starch slurry;
(2) Uniformly mixing a coupling agent and pure water, adding inorganic salt whisker, heating to 90-95 ℃, and shearing at a high speed to obtain modified inorganic salt whisker slurry;
(3) Firstly, uniformly mixing thermoplastic starch slurry, modified calcium sulfate whisker slurry and a composite antioxidant, then adding polyethylene resin and polyamide resin at 120-125 ℃, and then carrying out microwave treatment in a high-speed shearing process to obtain a mixed material;
(4) And (3) delivering the mixed material into a double-screw extruder for extrusion granulation and drying to obtain the degradable plastic mixed particles.
2. The preparation method of the degradable plastic mixed particles according to claim 1, wherein the polyethylene resin, the polyamide resin, the pullulan, the inorganic salt whisker, the plasticizer, the coupling agent, the composite antioxidant and the pure water are calculated according to mass percent: 25 to 28 percent of polyethylene resin, 21 to 23.5 percent of polyamide resin, 16 to 18 percent of amylopectin, 7 to 10 percent of plasticizer, 3.7 to 4.2 percent of inorganic salt whisker, 2.2 to 2.7 percent of coupling agent, 0.3 to 0.4 percent of compound antioxidant and the balance of pure water; wherein the pure water quality of the step (1) is twice the pure water quality of the step (2).
3. The method for preparing the degradable plastic mixed particles according to claim 1, wherein in the step (3), the high-speed shearing time is 90-120 min, and the microwave treatment is carried out every 10-15 min in the high-speed shearing process, the time of each microwave treatment is 2-3 min, and the microwave power is 20-25 KHz.
4. The method of claim 1, wherein in the step (1), the gelatinization temperature is 85 to 90 ℃ and the gelatinization time is 25 to 30min.
5. The method for producing a degradable plastic composite particle according to claim 1, wherein in the step (1), the time of high-speed shearing is 80 to 90 minutes; in the step (2), the time of high-speed shearing is 120-150 min.
6. The method for preparing the degradable plastic mixed particles according to claim 1 or 2, wherein the inorganic salt whisker is calcium sulfate whisker or basic magnesium sulfate whisker.
7. The method for preparing the degradable plastic mixed particles according to claim 1 or 2, wherein the plasticizer is polyethylene glycol or acetyl tributyl citrate.
8. The method for preparing the degradable plastic mixed particles according to claim 1 or 2, wherein the coupling agent is one of silane coupling agent K-450, titanate coupling agent HY311W or maleic anhydride.
9. The method for preparing the degradable plastic mixed particles according to claim 1 or 2, wherein the composite oxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 3:1.
10. The method for producing a degradable plastic composite particle according to claim 1, wherein in the step (4), extrusion conditions are: the extrusion temperature is 170-180 ℃, and the extrusion pressure is 85-90 MPa.
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| CN101092508A (en) * | 2007-06-26 | 2007-12-26 | 南京立汉化学有限公司 | Method for preparing low bending strength nylon 6 / polyethylene alloy |
| CN112251012A (en) * | 2020-10-22 | 2021-01-22 | 成都新柯力化工科技有限公司 | Method for preparing degradable plastic master batch by soluble salt-assisted plasticizing amylose |
| CN114133705A (en) * | 2021-07-09 | 2022-03-04 | 四川晶应新材料技术有限公司 | Preparation method of degradable plastic mixed particles |
| CN116876070A (en) * | 2023-07-25 | 2023-10-13 | 山东蓝海晶体科技有限公司 | Preparation method of calcium sulfate whisker |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092508A (en) * | 2007-06-26 | 2007-12-26 | 南京立汉化学有限公司 | Method for preparing low bending strength nylon 6 / polyethylene alloy |
| CN112251012A (en) * | 2020-10-22 | 2021-01-22 | 成都新柯力化工科技有限公司 | Method for preparing degradable plastic master batch by soluble salt-assisted plasticizing amylose |
| CN114133705A (en) * | 2021-07-09 | 2022-03-04 | 四川晶应新材料技术有限公司 | Preparation method of degradable plastic mixed particles |
| CN116876070A (en) * | 2023-07-25 | 2023-10-13 | 山东蓝海晶体科技有限公司 | Preparation method of calcium sulfate whisker |
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