CN117801484A - Polylactic acid-based coated paper recycling material, preparation method and product thereof - Google Patents
Polylactic acid-based coated paper recycling material, preparation method and product thereof Download PDFInfo
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- CN117801484A CN117801484A CN202311857336.5A CN202311857336A CN117801484A CN 117801484 A CN117801484 A CN 117801484A CN 202311857336 A CN202311857336 A CN 202311857336A CN 117801484 A CN117801484 A CN 117801484A
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- polylactic acid
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- 239000000463 material Substances 0.000 title claims abstract description 128
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 84
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 83
- 238000004064 recycling Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 229920003023 plastic Polymers 0.000 claims description 26
- 239000004033 plastic Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- 230000008878 coupling Effects 0.000 claims description 14
- 238000010168 coupling process Methods 0.000 claims description 14
- 238000005859 coupling reaction Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical group CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000002023 wood Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 5
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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 4
- 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 4
- -1 poly butylene succinate Polymers 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 229920002961 polybutylene succinate Polymers 0.000 claims description 2
- 239000004631 polybutylene succinate Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 14
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011091 composite packaging material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000010816 packaging waste Substances 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001896 polybutyrate Polymers 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a polylactic acid-based coated paper recycling material, a preparation method and a product thereof, wherein the polylactic acid-based coated paper recycling material is prepared from the following raw materials in parts by weight: 100 parts of polylactic acid-based laminated paper reclaimed materials, 2-10 parts of toughening agents, 0.3-0.8 part of thermo-oxidative stabilizers, 0.3-1 part of coupling agents, 0.2-0.5 part of chain extenders and 0.5-1 part of other auxiliary agents; wherein, the polylactic acid-based coated paper reclaimed material is crushed into cotton-shaped coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: 1, and a morphology of the crushed material in the range of 1. The polylactic acid-based coated paper recycling material has good comprehensive performance, can be produced by continuous granulation, realizes the reutilization of waste materials and reduces environmental pollution.
Description
Technical Field
The invention belongs to the field of resource recycling, and particularly relates to a polylactic acid-based coated paper recycling material, a preparation method thereof and a product thereof.
Background
The laminated paper composite packaging material has the characteristics of leakage prevention, light weight, easy processing and forming, low cost and the like, and is widely applied to packaging products such as catering, medicines, cosmetics, gifts and the like. The packaging waste contains a large amount of energy materials such as paper, plastic and the like, and huge resource waste and heavy environmental load are generated. The environmental pollution caused by the increasing number of composite packaging wastes is receiving more attention.
The composite packaging material waste mainly comes from two aspects, (1) a certain amount of waste films, waste materials and leftover materials are generated in the production process. (2) The waste discarded after use. At present, the recycling and utilization of these composite packaging wastes are very difficult, and are embodied in several aspects: 1. the production process is complex, the composite packaging material generally adopts a dry type, wet type, extrusion, hot melting and other composite modes, and the combination of the material components is tight, even the material components are integrated, so that the material components are difficult to separate by adopting a general method, and the recycling is very difficult. 2. The separation is difficult, the composite material packaging waste is particularly dispersed, and many waste materials are also existed in the waste, so that the recycling is difficult, the recycling mode can only adopt a low-level treatment mode, the recycling efficiency is low, the value is low, and the recycling is greatly limited.
The current recycling method of the laminated paper mainly comprises a landfill method, an incineration method and recycling. The recycling and reutilization mainly comprises a direct regeneration technology and a paper-plastic separation technology. The direct regeneration technology mainly comprises two technologies, namely a plastic wood technology (paper-plastic composite packaging is directly crushed and extrusion molded into a new plastic wood material) and a color music board technology (paper-plastic composite material is directly crushed and hot pressed into a color music board). The paper-plastic separation technology is to separate paper from plastic in the waste paper-plastic composite material and then recover the paper and plastic one by one.
However, for the paper-plastic separation technology, because of the specificity of the paper-plastic composite packaging material, the paper and the plastic are respectively recovered from the mixture, the problem of difficult separation of the paper-plastic and the high polymer exists, the process is extremely complex, and the production index requirement is high. For the direct regeneration technique, however, the following disadvantages exist: the crushed particles are large, the damage to paper fibers is large, the material performance is low, the bulk density of the crushed materials is high, and the crushed materials cannot be subjected to subsequent processing granulation.
Disclosure of Invention
The invention aims to overcome the defects in the direct regeneration technology and provide a polylactic acid-based coated paper recycling material, a preparation method and a product thereof.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a polylactic acid-based coated paper recycling material, which is prepared from the following raw materials in parts by weight: 100 parts of polylactic acid-based laminated paper reclaimed materials, 2-10 parts of toughening agents, 0.3-0.8 part of thermo-oxidative stabilizers, 0.3-1 part of coupling agents, 0.2-0.5 part of chain extenders and 0.5-1 part of other auxiliary agents; wherein, the polylactic acid-based coated paper reclaimed material is crushed into cotton-shaped coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: 1, and a morphology of the crushed material in the range of 1.
Preferably, the polylactic acid-based coated paper recycling material is a coated paper recycling material mainly comprising polylactic acid or modified polylactic acid.
Preferably, the toughening agent is at least one of acrylic acid ester toughening agent, poly (butylene succinate) and poly (butylene adipate terephthalate); the thermal oxygen stabilizer is at least one of calcium stearate, zinc stearate, antioxidant 1010 and antioxidant 168; the coupling agent is one of silane coupling agents KH540, KH550, KH560 and KH 570; preferably a silane coupling agent KH550; the chain extender is one of an ADR4468 and an ADR 4400; the other auxiliary agent is a composition of a lubricant and a plasticizer, wherein the lubricant is 0.3-0.5 part, and the toughening agent is 0.2-0.5 part; wherein the lubricant is at least one of oxidized polyethylene wax and EBS; the plasticizer is tributyl citrate.
In a second aspect, the invention provides a method for preparing the polylactic acid-based coated paper recycling material according to the first aspect, which comprises the following steps:
s1, crushing: the polylactic acid-based coated paper reclaimed material is crushed into cotton-like coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: 1;
s2, coupling, dispersing and mixing: performing coupling dispersion treatment on the crushed material, the thermo-oxidative stabilizer, the coupling agent and the chain extender obtained in the step S1 at a preset temperature and a preset rotating speed, and then adding the toughening agent and other auxiliary agents to uniformly mix;
s3, granulating: granulating the material obtained in the step S2 at a preset temperature and a preset rotating speed;
s4, cooling: cooling the material obtained in the step S3;
s5, granulating: and (3) granulating the aggregate obtained in the step (S4), and cooling and screening to obtain the polylactic acid-based coated paper recovery material.
Preferably, in the step S1, one of a non-plastic pulverizer with a mesh larger than 10 meshes and a plastic pulverizer with a mesh larger than 10 meshes is adopted for crushing, and the working temperature of the crushing is controlled below 45 ℃; preferably, step S1 is carried out by using a wood pulverizer having a mesh size of 20 mesh or more.
Preferably, the step S2 is carried out in a high-speed mixer, the crushed material obtained in the step S1, the thermo-oxidative stabilizer, the coupling agent and the chain extender are added at the temperature of not higher than 50 ℃, the coupling dispersion treatment is carried out for 5-15 minutes at the temperature of not higher than 70 ℃ and the rotating speed of more than 800 revolutions per minute, and then the toughening agent and other auxiliary agents are added and mixed uniformly.
Preferably, step S3 is to perform pelletization in a pelletizer or a high speed mixer, wherein: when the step S3 is carried out in the granulator, the temperature is 50-60 ℃, the rotating speed is 400-800 revolutions per minute, and the time is 3-5 min; when the step S3 is carried out in the high-speed mixer, the temperature is 100-120 ℃, the rotating speed is 800-1200 rpm, and the time is 5-10min.
Preferably, step S4 is carried out in a low speed mixer at a speed of 100-150 rpm and cooled to below 45 ℃ with stirring.
Preferably, step S5 is granulation in a twin screw granulator, wherein the twin screw granulator has a hopper with a stirrer and a hollow spring feed screw; preferably, the granulating temperature in step S5 is 160-190 ℃ and the screw speed is 180-400 rpm when granulating in a twin-screw granulator.
In a third aspect, the present invention also provides a polylactic acid-based coated paper recycling material product, which is made of the polylactic acid-based coated paper recycling material of the first aspect.
The beneficial effects of the invention are that the invention comprises: according to the invention, the recovered polylactic acid-based coated paper is crushed into cotton-shaped coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: the crushed material with the form within the range of 1 is mixed with specific amount of toughening agent, thermo-oxidative stabilizer, coupling agent, chain extender and other auxiliary agent in a dispersing way, granulated, cooled and granulated to obtain the polylactic acid-based coated paper recovery material with good comprehensive performance. The invention prepares a biodegradable new material with good comprehensive performance by applying the existing coated paper waste resource material and matching with other auxiliary agents and materials through a simple processing means, and can realize sustainable granulation production, thereby realizing the reutilization of waste materials and reducing environmental pollution.
Drawings
FIG. 1 is a schematic illustration of the polylactic acid-based coated paper regrind used in each of the comparative examples and examples of the present invention;
FIG. 2 is a schematic view of a crushed material denoted by P1 obtained in comparative example 1 of the present invention;
FIG. 3 is a schematic view of the crushed material denoted by P4 obtained in example 2 of the present invention;
FIG. 4 is a fiber morphology diagram of the crushed material denoted by P4 obtained in example 2 of the present invention at a magnification of 50 times by an electron microscope;
FIG. 5 is a schematic view of the PLA laminated paper recycling material obtained in example 2 of the invention;
FIG. 6 is a schematic diagram of a crushed material denoted by P3 obtained in example 3 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention and its application, in which embodiments and features of embodiments described herein may be combined with one another without conflict.
The polylactic acid-based laminated paper comprises a paper base and a laminated layer compounded with the paper base into a whole, wherein the laminated layer is a polylactic acid (PLA) base. The polylactic acid-based coated paper recycling material refers to waste films, waste materials, leftover materials and the like of the polylactic acid-based coated paper.
The embodiment of the invention provides a polylactic acid-based coated paper recycling material which is prepared from the following raw materials in parts by weight: 100 parts of polylactic acid-based laminated paper reclaimed materials, 2-10 parts of toughening agents, 0.3-0.8 part of thermo-oxidative stabilizers, 0.3-1 part of coupling agents, 0.2-0.5 part of chain extenders and 0.5-1 part of other auxiliary agents; wherein the polylactic acid-based coated paper recycled material is crushed into cotton-like coated paper fibers, the length (average length) of the paper fibers is less than 450 mu m, and the length-to-width ratio (average length-to-width ratio) is 25-50: 1, and a morphology of the crushed material in the range of 1.
In a preferred embodiment, the polylactic acid-based coated paper recycling material is a coated paper recycling material mainly comprising polylactic acid or modified polylactic acid.
In a preferred embodiment, the toughening agent is at least one of an acrylate toughening agent, polybutylene succinate, polybutylene terephthalate.
In a preferred embodiment, the thermo-oxidative stabilizer is at least one of calcium stearate, zinc stearate, antioxidant 1010, antioxidant 168.
In a preferred embodiment, the coupling agent is one of silane coupling agents KH540, KH550, KH560, KH 570; further preferred is a silane coupling agent KH550.
In a preferred embodiment, the chain extender is one of the chain extenders ADR4468, ADR 4400.
In a preferred embodiment, the other auxiliary agent is a combination of a lubricant and a plasticizer, wherein the lubricant is 0.3-0.5 part, and the toughening agent is 0.2-0.5 part; wherein the lubricant is at least one of oxidized polyethylene wax and EBS; the plasticizer is tributyl citrate.
The invention also provides a preparation method of the polylactic acid-based coated paper recycling material, which comprises the following steps:
s1, crushing: the polylactic acid-based coated paper reclaimed material is crushed into cotton-like coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: 1;
s2, coupling, dispersing and mixing: performing coupling dispersion treatment on the crushed material, the thermo-oxidative stabilizer, the coupling agent and the chain extender obtained in the step S1 at a preset temperature and a preset rotating speed, and then adding the toughening agent and other auxiliary agents to uniformly mix;
s3, granulating: granulating the material obtained in the step S2 at a preset temperature and a preset rotating speed;
s4, cooling: cooling the material obtained in the step S3;
s5, granulating: and (3) granulating the aggregate obtained in the step (S4), and cooling and screening to obtain the polylactic acid-based coated paper recovery material.
In the preferred embodiment, in the step S1, one of a non-plastic pulverizer with a mesh larger than 10 meshes and a plastic pulverizer with a mesh larger than 10 meshes is adopted for crushing, and the working temperature of the crushing is controlled below 45 ℃; preferably, the non-plastic pulverizer adopted in the step S1 is a wood pulverizer with a mesh opening of 20 meshes or more.
In the above preferred technical scheme, the wood pulverizer or plastic pulverizer used for the pulverizing is a non-cutting type device with cooled impact type blades, so that the damage to paper fibers can be reduced to the greatest extent, and the damage to the paper fibers caused by the cutting type pulverizing of the plastic pulverizer is avoided, thereby achieving the fiber length and the aspect ratio required by the invention. Further, the use of a screen larger than 10 mesh, more preferably 20 mesh or more ensures the fineness of the particles after pulverization. Table 1 below shows the fiber morphology parameters for the disintegration using different equipment:
table 1: fiber morphology parameters of different disintegrates
In a preferred embodiment, step S2 is carried out in a high-speed mixer, the crushed material obtained in step S1, the thermo-oxidative stabilizer, the coupling agent and the chain extender are added at a temperature not higher than 50 ℃, the coupling dispersion treatment is carried out at a temperature not higher than 70 ℃ and a rotation speed of more than 800 revolutions per minute for 5-15 minutes, and then the toughening agent and other auxiliary agents are added and mixed uniformly.
In the coupling dispersion treatment process, a thermo-oxidative stabilizer, a coupling agent and a chain extender are added in the early stage (at the temperature not higher than 50 ℃), so that the possibility of material performance reduction and color yellowing caused by decomposition of PLA due to heating in the coupling dispersion treatment process is avoided, and after the high-speed rotation dispersion treatment by a high-speed mixer, a toughening agent and other auxiliary agents are added for uniform mixing, so that the cotton-shaped coated paper fiber is completely uniformly dispersed.
In a preferred embodiment, step S3 is to perform pelletization in a pelletizer or a high speed mixer, wherein: when the step S3 is carried out in the granulator, the temperature is 50-60 ℃, the rotating speed is 400-800 revolutions per minute, and the time is 3-5 min; when the step S3 is carried out in the high-speed mixer, the temperature is 100-120 ℃, the rotating speed is 800-1200 rpm, and the time is 5-10min.
By granulating in the granulator or the high-speed mixer, the volume of the materials is effectively reduced, so that the feeding is not bridged during granulation, and the purpose of continuous production is realized. More preferably, the step S3 adopts the steps of granulating in a high-speed mixer, namely, coupling dispersion and mixing in the high-speed mixer in the step S2 and granulating operation in the step S3, so that secondary feeding brought by other granulating equipment is reduced, and the purposes of completing dispersion coupling treatment and granulating to reduce the volume of the material at one time can be realized.
In a preferred embodiment, step S4 is carried out in a low speed mixer, cooled to below 45℃with stirring at low speed (100-150 rpm).
After the pelletization operation in the step S3, the temperature of the material can reach 80-90 ℃, and the material is stirred and cooled at a low speed by being discharged into a low-speed mixer so as to be subjected to subsequent pelletization.
In a preferred embodiment, step S5 is granulation in a twin screw granulator, wherein the twin screw granulator has a hopper with a stirrer and a hollow spring feed screw; preferably, the granulating temperature in step S5 is 160-190 ℃ and the screw speed is 180-400 rpm when granulating in a twin-screw granulator.
When granulating in the double-screw granulator, the bridging can be further avoided from influencing the production by stirring of a stirrer arranged on a hopper; the hollow spring feeding screw can ensure that irregular aggregate can realize continuous feeding under the condition of not being hindered by any, thus ensuring continuous production, reasonable granulation processing temperature and screw rotating speed and ensuring plasticization of materials and dispersion of paper fibers.
The embodiment of the invention also provides a polylactic acid-based coated paper recycling material product, which is prepared from the polylactic acid-based coated paper recycling material.
In some embodiments, the polylactic acid-based coated paper recycled material article may be, for example, a 3D printed product, an injection molded product (such as a cutlery, a spoon, a golf tee, etc.), an extruded product (such as a floor, a tray, a plastic stool, a fence, etc.).
The invention is further illustrated by the following examples and comparative examples.
Comparative example 1
The polylactic acid-based laminated paper recycling material comprises the following raw materials in parts by weight: 100 parts of polylactic acid-based laminated paper reclaimed materials (shown in figure 1), 3 parts of FM40 toughening agents, 0.3 part of thermal oxygen stabilizers (the thermal oxygen stabilizers consist of 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168), 0.3 part of KH550 silane coupling agents, 0.2 part of chain extenders (chain extender ADR4468 produced by BASF), and 0.5 part of other auxiliary agents (the other auxiliary agents consist of 0.3 part of oxidized polyethylene wax and 0.2 part of tributyl citrate).
The polylactic acid-based coated paper recycled material was broken down into a broken material designated P1 in table 1 (as shown in fig. 2). In specific implementation, the PLA-based coated paper reclaimed material is cut into crushed materials with the code number P1 in table 1 by using a plastic crusher, and then the raw materials are put into a high-speed mixer according to the formula to be mixed, and discharged after being uniformly mixed, wherein the discharging temperature is not higher than 50 ℃. Putting into a double-screw granulator for bracing and granulating, wherein during granulating, bridging occurs due to large volume of materials, discharging is difficult, discharging is realized by continuous stirring manually, during bracing and granulating, continuous processing cannot be realized, a material sample is dried after granulating, and a sample strip is molded for performance test.
Comparative example 2
The raw material composition of the polylactic acid-based coated paper recovery material was the same as comparative example 1.
The polylactic acid-based coated paper regrind was broken down into broken pieces labeled P6 in table 1. The specific implementation method comprises the following steps:
s1, directly feeding the recovered material of the coated paper into a wood grinder with a sieve mesh of 10 meshes for grinding, wherein the grinding working temperature is controlled below 45 ℃, and the obtained grinding material with the code number P6 in the table 1 is obtained;
s2, putting the crushed materials into a high-speed mixer, adding a thermal oxygen stabilizer, a coupling agent and a chain extender according to the formula, setting the temperature of the high-speed mixer to 120 ℃, carrying out coupling dispersion treatment at the rotating speed of the mixer of 800 revolutions per minute, and adding a toughening agent and other auxiliary agents when the temperature of the materials is increased to 60-70 ℃, and continuing high-speed mixing;
s3, in the telling mixer in the step S2, observing the material pelleting condition when the material reaches about 80 ℃, and when pelleting begins to appear, adjusting to a low speed of 500 r/min and discharging to the low speed mixer;
s4, cooling to below 45 ℃ in a low-speed mixer;
s5, putting the cooled material of S4 into a double-screw granulator with an agitator and a hollow spring screw for granulation, setting the granulation temperature from a feeding machine head to 160-185 ℃, setting the rotation speed of the double screw to 200 revolutions per minute, cooling and granulating after double-screw extrusion, and drying to obtain the PLA coated paper recovery material.
Example 1
The raw material composition of the polylactic acid-based coated paper recovery material was the same as comparative example 1.
The polylactic acid-based coated paper regrind was broken down into broken pieces identified by the code number P5 in table 1. In the embodiment, according to the above formulation, unlike comparative example 2, the crushing in step S1 was performed by using a 20 mesh wood crusher to obtain crushed materials denoted by P5 in table 1, and the other steps S2 to S5 were the same as comparative example 2, and the morphology of the obtained PLA coated paper recovered materials was the same as that shown in fig. 5.
Example 2
The raw material composition of the polylactic acid-based coated paper recovery material was the same as comparative example 1.
The polylactic acid-based coated paper regrind was broken down into a crushed material designated P4 in table 1 (as shown in fig. 3 and 4). In the embodiment, according to the above formulation, unlike comparative example 2, the crushing in step S1 was performed by using a 30 mesh wood crusher to obtain crushed materials denoted by P4 in table 1, the high speed mixer in step S2 was rotated at 1200 rpm, and the twin screw in step S5 was rotated at 400 rpm, and the other materials were the same as comparative example 2, and the obtained PLA coated paper recycling material was shown in fig. 5.
Example 3
The raw material composition of the polylactic acid-based coated paper recovery material was the same as comparative example 1.
The polylactic acid-based coated paper regrind was broken down into a crushed material designated P3 in table 1 (as shown in fig. 6). In the embodiment, according to the above formulation, unlike comparative example 2, the recycled material of the coated paper in step S1 was fed into a plastic mill with mesh 30 mesh to be crushed, the crushed material denoted by P3 in table 1 was obtained, and the other steps S2 to S5 were the same as those in example 2, and the morphology of the recycled material of the PLA coated paper was as shown in fig. 5.
Example 4
The polylactic acid-based laminated paper recycling material comprises the following raw materials in parts by weight: 100 parts of polylactic acid-based laminated paper recycled material, 7 parts of a toughening agent (consisting of 2 parts of an FM40 toughening agent and 5 parts of a PBAT toughening agent), 0.5 part of a thermo-oxidative stabilizer (zinc stearate), 0.3 part of a KH550 silane coupling agent, 0.2 part of a chain extender (chain extender ADR4468 produced by BASF), and 0.6 part of other auxiliary agents (the other auxiliary agents consist of 0.3 part of oxidized polyethylene wax and 0.3 part of tributyl citrate).
The polylactic acid-based coated paper regrind was broken down into broken pieces identified by the code number P4 in table 1. In the embodiment, according to the above formulation, unlike in example 2, the rotation speed of the high-speed mixer in step S2 is 1000 rpm, the twin-screw granulation temperature in step S5 is 160-180 ℃, the twin-screw rotation speed is 300 rpm, and the other components are the same as in example 2, and the form of the recovered PLA coated paper is as shown in fig. 5.
Example 5
The raw material composition of the polylactic acid-based coated paper recycling material differs from that of example 4 in that: 10 parts of toughening agent (comprising 5 parts of FM40 toughening agent and 5 parts of PBAT toughening agent) and the same with example 4.
The polylactic acid-based coated paper regrind was broken down into broken pieces identified by the code number P4 in table 1. In the embodiment, the PLA coated paper recovered material obtained in the same manner as in example 4 according to the above formulation was as shown in fig. 5.
The physical properties of each comparative example and example of the present invention are shown in Table 2.
Table 2: physical Properties of comparative examples and examples of the present invention
In the embodiment of the invention, the preparation method changes the conventional mixing treatment mode in the industry, reduces the volume of the crushed coated paper recycled material, ensures that bridging and breakage are not generated in the processing process by adopting undetermined feeding equipment, and can be continuously granulated for production. By utilizing the method in the specific embodiment of the invention, not only is the polylactic acid-based coated paper recycling material prepared, but also the invention effectively solves the problem of recycling the polylactic acid-based coated paper waste, and reduces the waste and environmental pollution caused by the waste.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention. In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "preferred embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Those skilled in the art may combine and combine the features of the different embodiments or examples described in this specification and of the different embodiments or examples without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The polylactic acid-based coated paper recycling material is characterized by being prepared from the following raw materials in parts by weight: 100 parts of polylactic acid-based laminated paper reclaimed materials, 2-10 parts of toughening agents, 0.3-0.8 part of thermo-oxidative stabilizers, 0.3-1 part of coupling agents, 0.2-0.5 part of chain extenders and 0.5-1 part of other auxiliary agents; wherein, the polylactic acid-based coated paper reclaimed material is crushed into cotton-shaped coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: 1, and a morphology of the crushed material in the range of 1.
2. The polylactic acid-based coated paper recycling material according to claim 1, wherein the polylactic acid-based coated paper recycling material is a coated paper recycling material based on polylactic acid or modified polylactic acid.
3. The polylactic acid-based coated paper recycling material according to claim 1, wherein:
the toughening agent is at least one of acrylic acid ester toughening agent, poly butylene succinate and poly butylene adipate terephthalate;
the thermal oxygen stabilizer is at least one of calcium stearate, zinc stearate, antioxidant 1010 and antioxidant 168;
the coupling agent is one of silane coupling agents KH540, KH550, KH560 and KH 570; preferably a silane coupling agent KH550;
the chain extender is one of an ADR4468 and an ADR 4400;
the other auxiliary agent is a composition of a lubricant and a plasticizer, wherein the lubricant is 0.3-0.5 part, and the toughening agent is 0.2-0.5 part; wherein the lubricant is at least one of oxidized polyethylene wax and EBS; the plasticizer is tributyl citrate.
4. A method for preparing the polylactic acid-based coated paper recycling material as set forth in any one of claims 1 to 3, comprising the steps of:
s1, crushing: the polylactic acid-based coated paper reclaimed material is crushed into cotton-like coated paper fibers, the length of the paper fibers is less than 450 mu m, and the length-width ratio is 25-50: 1;
s2, coupling, dispersing and mixing: performing coupling dispersion treatment on the crushed material, the thermo-oxidative stabilizer, the coupling agent and the chain extender obtained in the step S1 at a preset temperature and a preset rotating speed, and then adding the toughening agent and other auxiliary agents to uniformly mix;
s3, granulating: granulating the material obtained in the step S2 at a preset temperature and a preset rotating speed;
s4, cooling: cooling the material obtained in the step S3;
s5, granulating: and (3) granulating the aggregate obtained in the step (S4), and cooling and screening to obtain the polylactic acid-based coated paper recovery material.
5. The method for producing a recycled material for polylactic acid-based coated paper according to claim 4, wherein in step S1, one of a non-plastic pulverizer with a mesh of more than 10 and a plastic pulverizer with a mesh of more than 10 is used for pulverizing, and the working temperature of the pulverizing is controlled below 45 ℃; preferably, step S1 is carried out by using a wood pulverizer having a mesh size of 20 mesh or more.
6. The method for preparing a polylactic acid-based coated paper recycling material according to claim 4, wherein step S2 is performed in a high-speed mixer, the crushed material obtained in step S1, the thermo-oxidative stabilizer, the coupling agent and the chain extender are added at a temperature not higher than 50 ℃, the coupling dispersion treatment is performed at a temperature not higher than 70 ℃ and a rotational speed of more than 800 rpm for 5-15 minutes, and then the toughening agent and other auxiliary agents are added and mixed uniformly.
7. The method for producing a polylactic acid-based coated paper recycling material according to claim 4, wherein step S3 is to granulate in a granulator or a high-speed mixer, wherein:
when the step S3 is carried out in the granulator, the temperature is 50-60 ℃, the rotating speed is 400-800 revolutions per minute, and the time is 3-5 min;
when the step S3 is carried out in the high-speed mixer, the temperature is 100-120 ℃, the rotating speed is 800-1200 rpm, and the time is 5-10min.
8. The method for producing a recycled material for a polylactic acid-based coated paper according to claim 4, wherein step S4 is performed in a low-speed mixer at a rotational speed of 100 to 150 rpm and cooled to 45℃or lower with stirring.
9. The method for producing a polylactic acid-based coated paper recycling material according to claim 4, wherein step S5 is granulation in a twin-screw granulator having a hopper with a stirrer and a hollow spring type feed screw; preferably, the granulating temperature in step S5 is 160-190 ℃ and the screw speed is 180-400 rpm when granulating in a twin-screw granulator.
10. A polylactic acid-based coated paper recycling material product, characterized in that the product is made of the polylactic acid-based coated paper recycling material as set forth in any one of claims 1-3.
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