CN113321902B - Degradable plastic uptake tray and production process - Google Patents
Degradable plastic uptake tray and production process Download PDFInfo
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- CN113321902B CN113321902B CN202110543626.7A CN202110543626A CN113321902B CN 113321902 B CN113321902 B CN 113321902B CN 202110543626 A CN202110543626 A CN 202110543626A CN 113321902 B CN113321902 B CN 113321902B
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- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/10—Forming by pressure difference, e.g. vacuum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a degradable plastic tray and a production process thereof, which relate to the technical field of new materials and comprise the following components in parts by weight: pbs resin, graphene composite modified starch, a plasticizer, a nano inorganic filler, an antioxidant 1010, a lubricant, a titanate coupling agent and calcium carbonate. The technical key points are as follows: in the preparation process of the plastic tray prepared by the invention, the processing performance and the degradability of the degradable plastic tray can be obviously improved by introducing the graphene composite modified starch.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a degradable plastic tray.
Background
The plastic tray is widely applied to logistics transportation and daily production work, and is deeply loved by people due to the portability.
PBS enters the field of material research in the 90 s of the 20 th century and quickly becomes one of hot materials for research on general completely biodegradable plastics which can be widely popularized and applied, and compared with degradable plastics such as PCL, PHB, PHA and the like, PBS has the characteristics of low price, excellent mechanical property and the like; compared with PLA with a similar price, PBS has the characteristics of convenient processing, adaptability to the conventional plastic processing technology and good heat resistance, and the heat distortion temperature can exceed 100 ℃ (the heat resistance temperature of PLA is only about 60 ℃). In addition, the raw material source for PBS synthesis can be either petroleum resource or biomass resource, and therefore, the method has attracted high attention in science and technology and industry.
The invention discloses a plastic suction tray with a cleaning function in Chinese patent with publication number CN 109205005A, which comprises a tray body, wherein the tray body is made of pbs materials, the front surface of the tray body is provided with a storage groove and a cleaning groove, the bottom and the inner wall of the storage groove are provided with reinforcing ribs, the joint of the bottom and the inner wall of the storage groove is arc-shaped and is convenient to clean, a washing brush and an automatic water spraying device are arranged in the cleaning groove, the inner wall of the cleaning groove is provided with a clamping edge, the washing brush and the automatic water spraying device are fixed in the cleaning groove through the clamping edge and can be taken out at any time to clean the plastic suction tray, the automatic water spraying device consists of a water spraying head, a handheld rod and a water storage bottle, the water spraying head is connected with the water storage bottle through a water pipe, the handheld rod is provided with a switch button, one side of the cleaning groove is provided with a circular groove, and the circular groove is used for containing the water storage bottle, the invention can realize cleaning of the blister tray at any time, and keep the blister tray clean in the use process, but the degradation performance of the adopted pbs material is insufficient, and the mechanical property of the pure pbs material cannot better meet the increasing performance requirements of the blister tray.
With increasing attention on environmental protection, degradable materials are more and more commonly applied, however, for example, starch materials, polyvinyl alcohol materials, polylactic acid materials and the like have high degradation performance, but the degradation performance is high, the rheological property is relatively poor, so that the mechanical property is general, and the application requirement cannot be met, therefore, the processing performance of the degradable materials needs to be improved to a certain extent, and further, the mechanical property of the degradable materials is improved, and the application requirement is met.
Therefore, a new solution is needed to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a degradable blister tray which has the advantages of excellent mechanical property and higher degradation property.
The invention also aims to provide a production process of the degradable blister tray, which has the advantages of improving the structural performance of the degradable blister tray and enhancing the mechanical performance of the degradable blister tray.
In order to achieve the purpose, the invention provides the following technical scheme:
a degradable plastic tray comprises the following components in parts by weight: 85-95 parts of pbs resin, 25-30 parts of graphene composite modified starch, 3-6 parts of plasticizer, 18-25 parts of nano inorganic filler, 10100.2-0.8 part of antioxidant, 1-1.5 parts of lubricant, 0.6-1.2 parts of titanate coupling agent and 3-5 parts of calcium carbonate.
By adopting the technical scheme, the mechanical property and the degradability of the degradable blister tray can be obviously improved;
further preferably, the preparation method of the graphene composite modified starch comprises the following steps:
(1) uniformly dispersing graphene into vinyl trimethoxy silane ethanol solution, stirring at the rotating speed of 500r/min for 40min at normal temperature, then performing suction filtration, and drying to constant weight to obtain silanized graphene;
(2) uniformly dispersing starch into deionized water, adjusting the temperature to 90-95 ℃, and stirring for 30-40min under heat preservation to obtain starch slurry;
(3) sequentially mixing graphene, maleic anhydride and starch slurry together, and stirring at the rotating speed of 1000r/min for 35min to obtain mixed slurry;
(4) and (3) placing the mixed slurry between two parallel polar plates of a plasma treatment device for plasma treatment for 1min, and then drying, crushing, grinding and sieving to obtain the graphene composite modified starch.
By adopting the technical scheme, the mechanical property is improved under the condition of improving the degradability of the blister tray, and the introduction of the graphene composite modified starch improves the degradability, and simultaneously, the graphene material has higher adsorption property. However, the adsorption effect of a simple graphene material is not ideal, mainly due to the characteristic of easy agglomeration, so in order to fully exert the adsorption capacity of graphene, graphene needs to be treated to a certain extent, and then the graphene is compounded with starch particles to improve the dispersion performance of the graphene. The graphene and the starch particles are compounded and introduced into a plastic suction tray material system, so that the degradable performance can be improved, meanwhile, the rheological property of the material is further improved, the mechanical property is enhanced, and the reduction of the rheological property caused by the introduction of the pure starch particles is avoided, and the mechanical property is relatively poor.
Further preferably, the mixing mass ratio of the graphene to the vinyl trimethoxy silane ethanol solution is 1: 10;
the mass fraction of the vinyl trimethoxy silane ethanol solution is 8%.
By adopting the technical scheme, the vinyl trimethoxy silane is used for improving the surface performance of the graphene particles and enhancing the bonding performance between the graphene particles and the starch particles.
More preferably, the starch is corn starch or soybean starch, preferably corn starch;
the mixing mass ratio of the starch to the deionized water is 1: 6.
Through adopting above-mentioned technical scheme, the degradable performance that improves the blister supporting plate that can step forward adopts the corn starch particle of unique structure, can be better combine mutually with graphite alkene, form the complex body.
More preferably, the mixing mass ratio of the graphene to the maleic anhydride to the starch slurry is 1: 4: 40.
more preferably, the plasma treatment process is as follows: the processing gas is helium, the gas flow is 1L/min, and the processing voltage is 200V.
More preferably, the plasticizer is epoxidized soybean oil;
the nano inorganic filler is nano bentonite or nano silicon dioxide;
the lubricant is polyethylene wax or stearic acid.
A production process of a degradable blister tray comprises the following steps:
adding pbs resin, graphene composite modified starch, a plasticizer, a nano inorganic filler, an antioxidant 1010, a lubricant, a titanate coupling agent and calcium carbonate in corresponding parts by weight into a drying oven, drying for 35min at the drying temperature of 80 ℃, and adding into a stirrer to be uniformly mixed to obtain a dry mixed raw material;
adding the dry mixture into a double-screw extruder for melt extrusion to obtain a hot sheet;
and step three, forming the hot sheet by a plastic uptake machine, and cutting to obtain a product.
More preferably, the mixing and stirring speed in the stirrer is 2000 r/min.
More preferably, the parameters of the melt extrusion in the twin-screw extruder are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 185 ℃, the temperature of the third zone is 185 ℃, the temperature of the fourth zone is 190 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the machine head is 195 ℃, and the rotating speed of the screw is 25 r/min.
By adopting the technical scheme, the raw materials are subjected to melt extrusion processing according to specific melt extrusion parameters, so that the components can be uniformly dispersed, the comprehensive performance of the plastic tray material can be obviously improved, and the application field of the plastic tray material is widened.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation process of the plastic tray prepared by the invention, the processing performance and the degradability of the degradable plastic tray can be obviously improved by introducing the graphene composite modified starch;
(2) the dispersion uniformity of the graphene can directly influence the performance of the composite material, including mechanical property, processing performance and the like, and in order to enable the graphene to be uniformly dispersed, the graphene is modified and combined with starch particles, so that the dispersion of a complex is greatly improved, the rheological property of the material is improved, and the mechanical property and the degradation property of a plastic uptake tray are improved;
(3) the raw materials are subjected to melt extrusion processing by specific melt extrusion parameters, so that the components can be uniformly dispersed, the comprehensive performance of the blister tray material can be remarkably improved, and the application field of the blister tray material is widened.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1: a degradable plastic tray comprises the following components in parts by weight: 85-95 parts of pbs resin, 25-30 parts of graphene composite modified starch, 3-6 parts of plasticizer, 18-25 parts of nano inorganic filler, 10100.2-0.8 part of antioxidant, 1-1.5 parts of lubricant, 0.6-1.2 parts of titanate coupling agent and 3-5 parts of calcium carbonate. Further preferably, the preparation method of the graphene composite modified starch comprises the following steps:
(1) uniformly dispersing graphene into a vinyl trimethoxy silane ethanol solution, stirring at the normal temperature at the rotating speed of 500r/min for 40min, then performing suction filtration, and drying to constant weight to obtain silanized graphene;
(2) uniformly dispersing starch into deionized water, adjusting the temperature to 90-95 ℃, and stirring for 30-40min under heat preservation to obtain starch slurry;
(3) sequentially mixing graphene, maleic anhydride and starch slurry together, and stirring at the rotating speed of 1000r/min for 35min to obtain mixed slurry;
(4) and (3) placing the mixed slurry between two parallel polar plates of plasma treatment equipment for plasma treatment for 1min, and then drying, crushing, grinding and sieving to obtain the graphene composite modified starch. The mixing mass ratio of the graphene to the vinyl trimethoxy silane ethanol solution is 1: 10; the mass fraction of the vinyl trimethoxy silane ethanol solution is 8%. The starch is soybean starch; the mixing mass ratio of the starch to the deionized water is 1: 6. The mixing mass ratio of the graphene to the maleic anhydride to the starch slurry is 1: 4: 40. the plasma treatment process comprises the following steps: the processing gas is helium, the gas flow is 1L/min, and the processing voltage is 200V. The plasticizer is epoxidized soybean oil; the nano inorganic filler is nano silicon dioxide; the lubricant is polyethylene wax. The components and the corresponding parts by weight thereof are shown in table 1 and are prepared by the following steps:
adding pbs resin, graphene composite modified starch, a plasticizer, a nano inorganic filler, an antioxidant 1010, a lubricant, a titanate coupling agent and calcium carbonate in corresponding parts by weight into a drying oven, drying for 35min at the drying temperature of 80 ℃, and adding into a stirrer to be uniformly mixed to obtain a dry mixed raw material;
adding the dry mixture into a double-screw extruder for melt extrusion to obtain a hot sheet;
and step three, forming the hot sheet by a plastic uptake machine, and cutting to obtain a product.
More preferably, the mixing and stirring speed in the stirrer is 2000 r/min.
More preferably, the parameters of the melt extrusion in the twin-screw extruder are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 185 ℃, the temperature of the third zone is 185 ℃, the temperature of the fourth zone is 190 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the machine head is 195 ℃, and the rotating speed of the screw is 25 r/min.
Examples 2 to 10: a degradable blister tray, which is different from the embodiment 1 in that each component and the corresponding parts by weight are shown in table 1.
Table 1:
TABLE 1 Components and parts by weight of examples 1-10
Example 11: a degradable blister tray, which is different from the embodiment 1 in that the starch is corn starch.
Example 12: a degradable blister tray, which differs from embodiment 1 in that the lubricant is stearic acid.
Example 13: a degradable plastic uptake tray, which is different from the embodiment 1 in that the nano filler is nano bentonite.
Comparative example 1: a degradable plastic uptake tray, which is different from the embodiment 1 in that graphene composite modified starch is replaced by conventional soybean starch.
Comparative example 2: a degradable plastic uptake tray, which is different from the embodiment 1 in that graphene and soybean starch are replaced by physical mixing in a constant proportion.
Comparative example 3: a degradable blister tray, which is different from the embodiment 1 in that plasma treatment is not performed in the preparation process of the graphene composite modified starch.
Comparative example 4: the graphene composite modified starch is different from example 1 in that no lubricant is added.
Comparative example 5: the graphene composite modified starch is different from the graphene composite modified starch in example 1 in that no nano inorganic filler is added.
Test rheology Performance test
The rheological experiment is carried out on a double-tube extrusion capillary rheometer, the diameter of a capillary tube opening die is 1.0mm, the length-diameter ratio (L/D) is 16: 1, the testing temperature range is 120-260 ℃, the temperature deviation is +/-0.1 ℃, and the melting time is 10 min;
TABLE 2
| Viscous flow activation energy kJ/mol | |
| Example 1 | 19.68 |
| Example 11 | 19.75 |
| Example 12 | 19.63 |
| Example 13 | 19.71 |
| Comparative example 1 | 18.23 |
| Comparative example 2 | 18.72 |
| Comparative example 3 | 19.01 |
| Comparative example 4 | 19.42 |
| Comparative example 5 | 19.11 |
As can be seen from Table 2, the blister tray material prepared by the invention has excellent rheological property which can directly influence the processing property of the material, and the good fluidity is beneficial to the forming processing of the material, thereby obviously improving the comprehensive property of the blister tray.
Experiment two biodegradation experiment
The obtained product is dried and buried in wet soil by adopting a soil burying method, and the temperature is kept at 25-30 ℃ during the experiment. Taking out the sample from the soil after 90 days, cleaning, drying and weighing, and calculating the weight loss rate of the sample;
TABLE 3
| Mass loss rate% | |
| Example 1 | 10.55 |
| Example 11 | 11.06 |
| Example 12 | 10.83 |
| Example 13 | 10.97 |
| Comparative example 1 | 12.10 |
| Comparative example 2 | 10.11 |
| Comparative example 3 | 10.02 |
| Control group | 0.28 |
Control group: the difference from the example 1 is that the graphene composite modified starch is not added;
as can be seen from Table 3, the degradation performance of the blister trays prepared by the present invention was greatly improved. The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (9)
1. The degradable plastic tray is characterized by comprising the following components in parts by weight: 85-95 parts of pbs resin, 25-30 parts of graphene composite modified starch, 3-6 parts of plasticizer, 18-25 parts of nano inorganic filler, 10100.2-0.8 part of antioxidant, 1-1.5 parts of lubricant, 0.6-1.2 parts of titanate coupling agent and 3-5 parts of calcium carbonate;
the preparation method of the graphene composite modified starch comprises the following steps:
(1) uniformly dispersing graphene into a vinyl trimethoxy silane ethanol solution, stirring at the normal temperature at the rotating speed of 500r/min for 40min, then performing suction filtration, and drying to constant weight to obtain silanized graphene;
(2) uniformly dispersing starch into deionized water, adjusting the temperature to 90-95 ℃, and stirring for 30-40min under heat preservation to obtain starch slurry;
(3) sequentially mixing the silanized graphene, maleic anhydride and starch slurry together, and stirring at the rotating speed of 1000r/min for 35min to obtain mixed slurry;
(4) and (3) placing the mixed slurry between two parallel polar plates of a plasma treatment device for plasma treatment for 1min, and then drying, crushing, grinding and sieving to obtain the graphene composite modified starch.
2. The degradable plastic tray of claim 1, wherein the graphene and vinyltrimethoxysilane ethanol solution are mixed in a mass ratio of 1: 10;
the mass fraction of the vinyl trimethoxy silane ethanol solution is 8%.
3. The degradable blister tray of claim 1, wherein the starch is corn starch or soybean starch;
the mixing mass ratio of the starch to the deionized water is 1: 6.
4. The degradable blister tray of claim 1, wherein the silanized graphene, the maleic anhydride and the starch slurry are mixed in a mass ratio of 1: 4: 40.
5. the degradable blister tray of claim 1, wherein the plasma treatment process is: the processing gas is helium, the gas flow is 1L/min, and the processing voltage is 200V.
6. The degradable blister tray of claim 1, wherein the plasticizer is epoxidized soybean oil;
the nano inorganic filler is nano bentonite or nano silicon dioxide;
the lubricant is polyethylene wax or stearic acid.
7. The production process of the degradable plastic tray of any one of claims 1 to 6, comprising the following steps:
step 1: adding the pbs resin, the graphene composite modified starch, the plasticizer, the nano inorganic filler, the antioxidant 1010, the lubricant, the titanate coupling agent and the calcium carbonate in corresponding parts by weight into a drying oven for drying treatment for 35min, wherein the drying temperature is 80 ℃, and then adding the materials into a stirrer for uniformly mixing and stirring to obtain a dry mixed raw material;
adding the dry mixture into a double-screw extruder for melt extrusion to obtain a hot sheet;
and step three, forming the hot sheet by a plastic uptake machine, and cutting to obtain a product.
8. The process of claim 7, wherein the mixing speed of the blender is 2000 r/min.
9. The process for producing the degradable blister tray according to claim 7, wherein the melt extrusion parameters in the twin-screw extruder are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 185 ℃, the temperature of the third zone is 185 ℃, the temperature of the fourth zone is 190 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the machine head is 195 ℃, and the rotating speed of the screw is 25 r/min.
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| JP4235744B2 (en) * | 2002-08-30 | 2009-03-11 | 独立行政法人産業技術総合研究所 | Biodegradable resin composition |
| CN103709688A (en) * | 2013-12-26 | 2014-04-09 | 安徽聚美生物科技有限公司 | PBS (polybuthylenesuccinate) fully biodegradable material as well as preparation method and application thereof |
| CN104861210B (en) * | 2015-04-30 | 2017-09-29 | 亿帆鑫富药业股份有限公司 | A kind of starch base full biodegradable resin of hydrophobic stabilization and preparation method thereof |
| CN108384161A (en) * | 2018-01-28 | 2018-08-10 | 朱春英 | Graphene modified starch multifunctional composite and preparation method thereof |
| CN111925563A (en) * | 2020-08-19 | 2020-11-13 | 成都新柯力化工科技有限公司 | High-impact-resistance injection molding grade biological starch plastic and preparation method thereof |
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