CN117683333A - Biodegradable composite material and preparation method and application thereof - Google Patents
Biodegradable composite material and preparation method and application thereof Download PDFInfo
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- CN117683333A CN117683333A CN202311804813.1A CN202311804813A CN117683333A CN 117683333 A CN117683333 A CN 117683333A CN 202311804813 A CN202311804813 A CN 202311804813A CN 117683333 A CN117683333 A CN 117683333A
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- calcium carbonate
- biodegradable
- particles
- composite material
- biodegradable composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 83
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 229920003023 plastic Polymers 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims abstract description 16
- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 13
- 229920000704 biodegradable plastic Polymers 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 7
- 229920001896 polybutyrate Polymers 0.000 claims description 6
- 229910021532 Calcite Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000029087 digestion Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 3
- 238000012360 testing method Methods 0.000 description 12
- 229920006238 degradable plastic Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Abstract
The application discloses a biodegradable composite material and a preparation method and application thereof. The biodegradable composite material consists of heavy calcium particles, calcium carbonate whiskers and biodegradable resin. The biodegradable composite material has good mechanical property, good service performance and low cost; in addition, as the biodegradable material has better mechanical property, the area of the film plastic product which can be produced by the biodegradable composite material per ton of the biodegradable composite material is increased, and the cost of the film plastic product per unit area is further reduced.
Description
Technical Field
The application relates to the technical field of biodegradable materials, in particular to a biodegradable composite material and a preparation method and application thereof.
Background
The biodegradable plastic is an effective way for solving the environmental pollution caused by plastic waste, is a direction of developing disposable plastic products in the future, and has very broad market prospect.
From the present situation, biodegradable plastics are most used on conventional plastic articles such as packaging articles and disposable articles. In addition, markets worthy of development are various daily necessities, stationery, toys, construction products and medical plastic products. Because the few people entering in the fields at present are few, the market demand is large, and the added value is high. In addition, the usage amount of disposable plastic products such as desert control, barren mountain tree planting, city planning, various slope protection, soil fixing engineering and the like is greatly increased, and the method is a good opportunity for biodegradable plastics. The development of biodegradable packaging articles is also a future trend in the packaging industry. The problems of slow popularization and the like exist in the current field of degradable plastics, and the main reasons are that the production cost of the biodegradable plastics is 2 to 3 times that of the traditional plastic bags, the mechanical property is poor, the usability is poor, and the industrial propulsion speed is very slow.
Therefore, how to improve the mechanical property and the service performance while reducing the cost of the biodegradable plastic is a difficult problem in the technical field of biodegradable materials.
Disclosure of Invention
The purpose of the application is to provide a novel biodegradable composite material, and a preparation method and application thereof.
The application adopts the following technical scheme:
in one aspect, a biodegradable composite is disclosed, the biodegradable composite being comprised of heavy calcium particles, calcium carbonate whiskers, and a biodegradable resin.
It should be noted that, the biodegradable material of the present application combines the heavy calcium particles and the calcium carbonate whisker, and adds the composite into the degradable plastic system, thereby not only greatly reducing the cost of the biodegradable material, but also improving the mechanical property and the service performance of the biodegradable material, and effectively solving the popularization and application barrier of the biodegradable material.
In one implementation of the present application, the weight ratio of heavy calcium carbonate particles, calcium carbonate whiskers and biodegradable resin is (10-30): (20-40): (30-50).
In one implementation of the present application, the biodegradable resin is at least one of PBAT and PLA.
In one implementation of the present application, the heavy calcium particles are ground from calcite.
In one implementation of the present application, calcite is a particle having a D90 of less than 0.7 microns.
Another aspect of the present application discloses the use of the biodegradable composite of the present application for the preparation of biodegradable plastics.
In another aspect, the application discloses a preparation method of the biodegradable composite material, which comprises the steps of mixing heavy calcium particles, calcium carbonate whiskers and biodegradable resin, uniformly stirring to prepare a mixed material, and preparing the mixed material into plastic master batches, namely the biodegradable composite material.
In one implementation mode of the application, the heavy calcium carbonate particles and the calcium carbonate whiskers are modified heavy calcium carbonate particles and modified calcium carbonate whiskers which are subjected to modification treatment; the modification treatment comprises adding 0.5-1.5% of heavy calcium carbonate particles or calcium carbonate whiskers by weight into a coupling agent, stirring for 20-45 min at 90-105 ℃ at a stirring rate of 900-1100 r/min to obtain modified heavy calcium carbonate particles or modified calcium carbonate whiskers, wherein the coupling agent is titanate and/or aluminate.
In one implementation mode of the application, the preparation method of the calcium carbonate whisker comprises the steps of preparing superfine slurry from calcium oxide through digestion and superfine treatment, and performing carbonization reaction on the superfine slurry to obtain the calcium carbonate whisker.
In one implementation of the present application, digestion includes adding water to calcium oxide to prepare a slurry having a solids content of 10-30%, stirring at a speed of 15-60 revolutions per minute, and heating to 35-70 ℃.
In one implementation of the present application, the ultra-fine treatment comprises agitation milling of the slurry, wherein the milling media has a diameter of 2-8 mm, a filling rate of 60-80%, and an agitation rate of 300-1100 revolutions per minute.
In one implementation of the present application, the carbonization reaction involves introducing carbon dioxide into the ultra-fine treated slurry at a rate of 0.2 to 100 liters/min while stirring the slurry at 60 to 150 revolutions/min for 20 to 50 minutes.
The beneficial effects of this application lie in:
the biodegradable composite material has good mechanical property, good service performance and low cost; in addition, as the biodegradable material has better mechanical property, the area of the film plastic product which can be produced by the biodegradable composite material per ton of the biodegradable composite material is increased, and the cost of the film plastic product per unit area is further reduced.
Detailed Description
Aims at solving the problems of poor mechanical property, poor service performance, slow industrial propulsion speed and the like of the existing biodegradable material. The nano particle and whisker composite material is creatively adopted and added into a degradable plastic formula system, so that the cost is greatly reduced, and the mechanical property and the service performance are improved. Thoroughly solves the popularization and application obstacle of the degradable plastic.
In one implementation of the present application, calcite is specifically prepared as a particulate material having a D90 of less than 0.7 microns, i.e. the heavy calcium particles of the present application, by wet milling. And (3) utilizing calcium oxide, and further performing carbonization reaction on the superfine slurry prepared by digestion and superfine treatment to obtain the calcium carbonate whisker. Drying and modifying the two materials respectively, and storing the two materials respectively. Wherein, the modification treatment comprises adding the heavy calcium carbonate particles or the calcium carbonate whiskers into a coupling agent according to the weight of 0.5-1.5%, stirring for 20-45 minutes at the temperature of 90-105 ℃ and the stirring speed of 900-1100 r/min, thus obtaining the modified heavy calcium carbonate particles or the modified calcium carbonate whiskers, wherein the coupling agent is titanate and/or aluminate. For example, in one implementation of this example, 1% of coupling agent aluminate is specifically added, and the mixture is stirred for 30 minutes at a temperature of 100 ℃ and a stirring rate of 1000 revolutions per minute, so as to obtain modified heavy calcium carbonate particles and modified calcium carbonate whiskers, respectively.
According to a certain proportion, for example, 10 percent of heavy calcium particles, 40 percent of calcium carbonate whiskers and 50 percent of biodegradable resin, the superfine heavy calcium particle material, the calcium carbonate whiskers and the biodegradable resin (PBAT or PLA) are weighed, put into a high-speed mixer, and evenly mixed and stirred to finish the batching. The prepared material is then fed into a twin-screw granulator to produce degraded plastic mother particles, which can be directly used for manufacturing various plastic products, such as blown films. In the biodegradable composite material system, the heavy calcium particles play a role in particle dispersion strengthening, the calcium carbonate whiskers play a network structure, and the heavy calcium particles play a role in a solid dispersing agent.
The biodegradable composite material has the following advantages:
the materials in the material system are uniformly dispersed, the mechanical property of the product is good, the cost is low, the modulus of the product is high, therefore, the product has certain stiffness, in addition, the thickness of the prepared plastic product can be reduced due to the good mechanical property, the area of the plastic product such as a film made of ton raw materials is increased, and the cost of the plastic product is further reduced. In the comprehensive view, the biodegradable plastic prepared by the formula has low cost, good mechanical property and good service performance.
The present application is described in further detail below by way of specific examples. The following examples are merely illustrative of the present application and should not be construed as limiting the present application.
Example 1
10 kg of modified heavy calcium carbonate granular material, 40 kg of modified calcium carbonate whisker and 50 kg of PBAT are taken, put into a high-speed mixer for stirring for 10 minutes, and mixed and stirred uniformly, so as to finish batching, for example, the materials are added into the high-speed mixer for stirring for 10-25 minutes, the stirring speed is 500-900 revolutions per minute, and the stirring speed is particularly 700 revolutions per minute for 20 minutes. And then, the prepared materials enter a double-screw granulator to prepare degradable plastic master batches, and the test pieces are punched out to test the tensile strength and modulus.
The example adopts an HY-0580 microcomputer control electronic universal material testing machine, and comprises the following specific steps: preparing an international standard test spline from the master batch after granulation through an injection molding machine, fixing the spline on the testing machine by using a clamp, starting the testing machine to start stretching, and synchronously displaying the tensile strength value, wherein the data of the spline when the spline breaks is the tensile strength of the spline. And similarly, fixing the spline on a testing machine by using a clamp, starting the testing machine to perform bending stress test, wherein the data comprise applied stress and deformation values of the spline, and obtaining the elastic modulus of the spline by a computer in the instrument according to the stress/strain values.
The test results of this example show that the spline prepared from the biodegradable composite material has a tensile strength of 22.8Mpa and an elastic modulus of 246.8Mpa. In the example, the mechanical properties of the obtained sample can reach the tensile strength of a spline of 22.8Mpa and the elastic modulus of 246.8 Mpa; the existing common biodegradable plastic has the proportion of calcium carbonate, PBAT=20:80, the tensile strength of the test data is 13.1Mpa, and the elastic modulus is 148.3Mpa. As can be seen by comparison, the cost of the formulation is obviously lower than that of the conventional biodegradable plastic, but the mechanical property is obviously higher than that of the conventional formulation, that is, if the formulation is based on the same mechanical property, the thickness of the degradable plastic product (film and injection molding) prepared by the formulation can be thinner than that of the conventional formulation, that is, the film area can be larger, the number of injection molding pieces can be more, and the economic benefit is very obvious.
Further, in this example, the master batch is sent to a film blowing machine for film blowing, and the blown film is placed on a table top, so that a certain standing state can be seen, which indicates that the plastic film has a certain stiffness, that is, the specific expression of large modulus.
Comparative example 1
10 kg of modified nano calcium carbonate (namely modified heavy calcium carbonate particles in example 1) and 40 kg of PBAT are taken, put into a high-speed mixer for stirring for 10 minutes, and are uniformly mixed and stirred to finish the batching. And then, the prepared materials enter a double-screw granulator to prepare degradable plastic master batches, and the test pieces are punched out to test the tensile strength and modulus.
Tensile strength and modulus were measured in the same manner as in example 1, and the results showed. The tensile strength of the sample bars is only 15.2Mpa and the elastic modulus is only 197.5Mpa. Obviously, the tensile strength and the elastic modulus of the biodegradable material of this example are significantly reduced, unlike example 1. The modified heavy calcium particles are only added, and the tensile strength and the elastic modulus are higher than those of the conventional formula of 13.1Mpa and 148.3Mpa on the premise of the same formula proportion, but the mechanical properties of comparative example 1 still have a large gap, so that the whisker plays a latticed framework structure in the biodegradable plastic, and the whisker has a great contribution to the improvement of the mechanical properties, particularly the improvement of the modulus.
Further, the master batch of the example enters a film blowing machine to blow films, the blown films are placed on a table top, the films can be seen to be in a flat state, and the film has no stiffness. It is further illustrated that whiskers may exhibit an increase in stiffness in a film.
The foregoing is a further detailed description of the present application in connection with the specific embodiments, and it is not intended that the practice of the present application be limited to such descriptions. It will be apparent to those skilled in the art to which the present application pertains that several simple deductions or substitutions may be made without departing from the spirit of the present application.
Claims (10)
1. A biodegradable composite material, characterized in that: the biodegradable composite material consists of heavy calcium particles, calcium carbonate whiskers and biodegradable resin.
2. The biodegradable composite according to claim 1, characterized in that: the weight ratio of the heavy calcium particles to the calcium carbonate whiskers to the biodegradable resin is (10-30)/(20-40)/(30-50).
3. The biodegradable composite according to claim 1, characterized in that: the biodegradable resin is at least one of PBAT and PLA.
4. A biodegradable composite according to any one of claims 1-3, characterized in that: the heavy calcium particles are formed by grinding calcite;
preferably, the calcite is a particle having a D90 of less than 0.7 microns.
5. Use of the biodegradable composite material according to any one of claims 1-4 for the preparation of biodegradable plastics.
6. A method of preparing a biodegradable composite material according to any one of claims 1-4, characterized in that: the biodegradable composite material is prepared by mixing heavy calcium carbonate particles, calcium carbonate whiskers and biodegradable resin, uniformly stirring to prepare a mixed material, and preparing the mixed material into plastic master batches.
7. The method of manufacturing according to claim 6, wherein: the heavy calcium particles and the calcium carbonate whiskers are modified heavy calcium particles and modified calcium carbonate whiskers which are subjected to modification treatment;
the modification treatment comprises the steps of adding 0.5-1.5% of heavy calcium carbonate particles or calcium carbonate whiskers by weight of the heavy calcium carbonate particles or calcium carbonate whiskers into a coupling agent, stirring for 20-45 minutes at the temperature of 90-105 ℃ at the stirring speed of 900-1100 r/min, and obtaining modified heavy calcium carbonate particles or modified calcium carbonate whiskers, wherein the coupling agent is titanate and/or aluminate.
8. The method of manufacturing according to claim 6, wherein: the preparation method of the calcium carbonate whisker comprises the steps of preparing superfine slurry by digestion and superfine treatment of calcium oxide, and performing carbonization reaction on the superfine slurry to obtain the calcium carbonate whisker.
9. The method of manufacturing according to claim 8, wherein: the digestion includes adding water to calcium oxide to prepare a slurry with a solids content of 10-30%, stirring at a speed of 15-60 rpm, and heating to 35-70 ℃.
10. The preparation method according to any one of claims 7 to 9, characterized in that: the superfine treatment comprises stirring and grinding the slurry, wherein the diameter of a grinding medium is 2-8 mm, the filling rate is 60-80%, and the stirring speed is 300-1100 r/min;
preferably, the carbonization reaction comprises introducing carbon dioxide into the ultra-fine treated slurry at a rate of 0.2 to 100 liters/min while stirring the slurry at 60 to 150 revolutions/min for 20 to 50 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311804813.1A CN117683333A (en) | 2023-12-25 | 2023-12-25 | Biodegradable composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311804813.1A CN117683333A (en) | 2023-12-25 | 2023-12-25 | Biodegradable composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117683333A true CN117683333A (en) | 2024-03-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311804813.1A Pending CN117683333A (en) | 2023-12-25 | 2023-12-25 | Biodegradable composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117683333A (en) |
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2023
- 2023-12-25 CN CN202311804813.1A patent/CN117683333A/en active Pending
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