CN109627709B - Degradable bio-based master batch and preparation method and application thereof - Google Patents
Degradable bio-based master batch and preparation method and application thereof Download PDFInfo
- Publication number
- CN109627709B CN109627709B CN201811595857.7A CN201811595857A CN109627709B CN 109627709 B CN109627709 B CN 109627709B CN 201811595857 A CN201811595857 A CN 201811595857A CN 109627709 B CN109627709 B CN 109627709B
- Authority
- CN
- China
- Prior art keywords
- biodegradable polyester
- master batch
- bio
- biological filler
- degradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
Abstract
The invention relates to a degradable bio-based master batch, a preparation method and application thereof, and belongs to the field of modification of high polymer materials. The degradable bio-based master batch comprises biodegradable polyester and a biological filler, wherein the weight ratio of the biodegradable polyester to the biological filler is 20-40: 60-80 parts; the biological filler is from natural biomass resources, the total organic carbon in the biological filler accounts for more than 80 percent of the total carbon weight in the biological filler, and the particle size D of the biological filler500.5 to 8 μm; the total organic carbon in the degradable bio-based master batch accounts for 60-100% of the weight of the total carbon in the degradable bio-based master batch. The biodegradable polyester composition is good in biodegradability and excellent in mechanical property.
Description
Technical Field
The invention relates to a degradable bio-based master batch, a preparation method and application thereof, and belongs to the field of modification of high polymer materials.
Background
Biodegradable polyester is a high molecular material using biological resources as raw materials. Compared with petroleum-based polymers taking petrochemical resources as raw materials, the biodegradable polyester can be degraded in the biological or biochemical action process or biological environment, and is one of the most active degradation materials in the research of the current biodegradable plastics and the best market application.
Chinese patent CN 102597105a reports that biodegradable aliphatic-aromatic polyesters obtained starting from aliphatic diacids such as adipic acid, aromatic diacids such as terephthalic acid and aliphatic diols are known in the literature and on the market. The constituent monomers of these polymers are not renewable, so that they have a significant impact on the environment, regardless of their biodegradability.
Furthermore, such polyesters currently on the market have an amount of aromatic acids of less than 48 mol%, since above this threshold the percentage of biodegradation of these polyesters is significantly reduced. This significantly limits the use of polyester for high mechanical properties associated with compostability, for example for the manufacture of bags for collecting organic waste.
Composting is an industrial process that mimics the processes in nature that bring organic matter back to life cycle, reproducing these processes in a controlled and accelerated form. In nature, the organic matter that has been produced and is no longer living (leaves of dried trees, branches, animal remains, etc.) is decomposed by the microorganisms present in the soil, which return it to the natural circulation. The remaining, less degradable components constitute humus, which is therefore an important food provider for plants, in view of its ability to slowly but constantly release nutrient elements (nitrogen, phosphorus, potassium, etc.) to ensure sustained fertility of the ground. Industrial composting is therefore a process that provides a structure for the rational management of the microbial activities that occur spontaneously in nature, in order to reduce the time necessary to obtain a type of humus, i.e. composting, and to improve the quality of the final product with respect to the products obtained naturally.
Similarly, home composting is a process in which organic material from kitchen and garden food scraps is deposited in compost bins or dug holes in the ground and aerobically degraded under milder conditions than industrial composting. In particular, aerobic degradation in a home composting process is carried out at room temperature (typically 10 to 45 ℃).
However, in the prior art, the biodegradability is better and there are fewer biodegradable polyesters that can be used for composting.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a degradable bio-based master batch, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the degradable bio-based master batch comprises biodegradable polyester and a biological filler, wherein the weight ratio of the biodegradable polyester to the biological filler is (20-40): 60-80 parts; the biological filler is from natural biomass resources, the total organic carbon in the biological filler accounts for more than 80 percent of the total carbon weight in the biological filler, and the particle size D of the biological filler500.5 to 8 μm;
the total organic carbon in the degradable bio-based master batch accounts for 60-100% of the weight of the total carbon in the degradable bio-based master batch.
The Total Organic Carbon (TOC) content of the biological filler and the degradable biological base master batch can be obtained by testing according to ISO16620-2 standard. The method for testing the particle size of the biological filler in the degradable biological-based master batch comprises the following steps:
a) placing 2.0-3.0 g of the degradable bio-based master batch in a crucible;
b) placing the crucible filled with the degradable bio-based master batch in a muffle furnace, and firing for 30-45 minutes at 700 ℃;
c) the particle size of the residue after firing was measured according to the method of GB/T19077.1 "particle size analysis laser diffraction method".
The invention selects the biological filler with proper particle size to prepare the master batch, can prepare the high-filling (more than or equal to 65 percent) bio-based filling master batch, keeps the use performance of the master batch on the basis of reducing the master batch cost, and has better degradation performance when the master batch and other degradation materials form a composition.
The biological filler is difficult to agglomerate when the particle size is larger, and is favorable for dispersion in biodegradable polyester; but when the particle size D of the biological filler50When the particle size exceeds 8 μm, the particle size of the bio-filler is too large, and thus the particle size affects the surface properties (roughness) of the subsequent film and the like, thereby affecting the performance of the product.
As a preferred embodiment of the degradable bio-based masterbatch of the invention, the weight ratio of the biodegradable polyester to the biological filler is 25-35: 65-75. Researches show that the weight ratio of the biodegradable polyester to the biological filler can influence the biodegradation performance and the tear strength of the polyester composition containing the degradable biological-based master batch, and the biodegradation performance and the tear strength of the finally obtained polyester composition are more excellent within the preferred weight ratio range.
As a preferred embodiment of the degradable bio-based masterbatch of the invention, the biodegradable polyester has a melt index of 8-80g/10min measured according to ASTM D1238 using a weight of 2.16kg and at a temperature of 190 ℃; preferably, the biodegradable polyester has a melt index of 10 to 60g/10 min; more preferably, the biodegradable polyester has a melt index of 15 to 45g/10 min. The biodegradability and the tear strength of the polyester composition containing the degradable bio-based master batch of the invention are also influenced by the melt index of the biodegradable polyester in the master batch, when the melt index of the biodegradable polyester is 10-60g/10min, the biodegradability and the tear strength of the obtained polyester composition are better, and especially when the melt index of the biodegradable polyester is 15-45g/10min, the biodegradability and the tear strength of the obtained polyester composition are optimal.
As a preferred embodiment of the degradable bio-based master batch of the invention, the particle size D of the biological filler500.8 to 6 μm; more preferably, the biomass is biomassParticle diameter D of the filler501 to 5 μm.
As a preferred embodiment of the degradable bio-based masterbatch of the present invention, at least one of the following (a) to (b):
(a) the biodegradable polyester is at least one of polylactic acid, Polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene adipate-co-polybutylene succinate (PBSA), polybutylene adipate-terephthalate (PBAT), polybutylene succinate-terephthalate (PBST), and polybutylene sebacate-terephthalate (PBSeT);
(b) the biological filler is at least one of animal bone, eggshell, coral, shell, Concha Ostreae, and nacreous layer.
As a preferred embodiment of the degradable bio-based masterbatch, the preparation method of the biological filler is as follows: firstly, the particle diameter D is obtained by crushing and screening50Is a biological filler crude product with the particle size of 15-50 mu m; then crushing the crude product of the biological filler by an airflow crusher to obtain the biological filler; wherein, the conditions of the jet mill are as follows: the rotating speed of a grading wheel is 3000-5000 rpm, and the pressure of an induced draft fan is-0.3 to-0.1 MPa; the feeding amount is 15-32 kg/h.
In addition, the invention also provides a preparation method of the degradable bio-based master batch, which comprises the following steps: uniformly mixing the components in the degradable bio-based master batch according to a proportion, putting the mixture into a double-screw extruder, extruding and granulating at 140-220 ℃ to obtain the degradable bio-based master batch.
In addition, the invention also provides a biodegradable polyester composition, which comprises the following components in parts by weight: 50-90 parts of aliphatic polyester or aliphatic-aromatic copolyester, 0-35 parts of natural polymer, 5-40 parts of degradable bio-based master batch, 0-5 parts of inorganic filler and 0-4 parts of auxiliary agent.
The presence of aromatic monomers such as terephthalic acid in the aliphatic-aromatic copolyester in the above biodegradable polyester composition is relevant to obtain an aliphatic-aromatic copolyester having a sufficiently high melting temperature, a sufficient crystallization rate, relevant mechanical properties such as ultimate strength, puncture energy and elastic modulus, and excellent industrial processability characteristics. However, regardless of biodegradability, the synthetic origin of the monomers limits the application of these polyesters, for example, the possibility of significantly reducing the consumption of resources (raw materials) from non-renewable carbon.
On the other hand, a high content of aliphatic monomers of synthetic origin, such as adipic acid, although desirable for achieving a suitable level of biodegradability, not only increases the environmental impact of these polyesters but also worsens their mechanical properties. Furthermore, the high content of aliphatic monomers significantly reduces the melting temperature of the polyester and reduces its crystallization rate at high temperatures, thereby requiring the use of greater kcal and longer cooling times during industrial processing of the polyester. These limitations have a detrimental effect on the industrial processability of these polyesters.
The filler is one of the additives commonly used in plastics, and can maintain the good performance of the polyester composition by adding the filler, but the performance of the polyester composition is affected by adding the filler in too large an amount, and the adding amount of the filler in too high an amount is difficult to realize.
The aliphatic polyester, the aliphatic-aromatic copolyester and the polymer of natural origin adopted by the invention are all known on the market, and the biodegradable polyester composition obtained by combining the aliphatic polyester, the aliphatic-aromatic copolyester and the polymer of natural origin according to the specific proportion is good in biodegradability and has excellent mechanical properties. And, due to their excellent mechanical properties and biodegradability, said compositions are particularly suitable for the manufacture of films and film bags, such as: food packaging films and bags for collecting organic waste. The research shows that the longitudinal tearing strength of the 12 mu m +/-1 mu m film prepared by the biodegradable polyester composition is more than or equal to 1100mN according to the standard ASTM D-882/88, and the transverse tearing strength of the prepared 12 mu m +/-1 mu m film is more than or equal to 2800mN according to the standard ASTM D-882/88.
More importantly, the biodegradable polyester composition of the invention is compostable at home according to the italian standard UNI11355: 2010.
As a preferred embodiment of the biodegradable polyester composition of the present invention, at least one of the following (I) to (IV):
the aliphatic polyester is at least one of polybutylene succinate (PBS) and polybutylene adipate-co-polybutylene succinate (PBSA), and the aliphatic-aromatic copolymer is at least one of polybutylene adipate-terephthalate (PBAT), polybutylene succinate-terephthalate (PBST) and polybutylene sebacate-terephthalate (PBSeT);
(II) the polymer of natural origin is at least one of starch and polylactic acid;
(III) the inorganic filler is selected from at least one of talcum powder, montmorillonite, kaolin, graphite, gypsum, conductive carbon black, calcium chloride, ferric oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber and mineral fiber;
and (IV) the auxiliary agent is at least one of a plasticizer, a release agent, a surfactant, wax, an antistatic agent, a dye, a UV absorbent and a UV stabilizer.
Furthermore, the invention also provides a preparation method of the biodegradable polyester composition, which comprises the following steps: uniformly mixing the components in the biodegradable polyester according to a certain proportion, putting the mixture into a single-screw film blowing machine, blowing the film at the temperature of 120-180 ℃, or putting the mixture into an extruder after uniformly mixing, extruding and granulating at the temperature of 140-220 ℃ to obtain the biodegradable polyester.
Finally, the present invention also provides a film or film bag comprising the above biodegradable polyester composition. The biodegradable polyester composition of the present invention can be used for the preparation of films, film bags or other composites and the like, which are useful, for example, for the manufacture of (1) mono-and bi-oriented films, and films laminated in multiple layers with other polymeric materials, (2) films for agricultural applications, (3) cling films for food, and for wrapping waste, (4) seed dressing equipment, (5) glues, (6) bags for organic waste collection, (7) thermoformed single-layer and multi-layer food packaging, (8) multilayer laminates of layers obtained using extrusion coating methods, containing paper, plastic, aluminum or metallized films, (9) foamed or foamable beads for the manufacture of parts obtained by sintering, (10) foamed and semi-foamed products, including foam blocks formed using pre-foamed particles, (11) foam sheets and containers obtained therefrom for food packaging, (12) Fruit and vegetable containers, (13) composites containing gelatinized, disintegrated and/or compounded starch, natural starch, flour or natural fillers of plants or inorganic materials, (14) fibers, wherein the core is composed of a rigid polymer; blended composite fibers having fibers of different cross-sections from round to multilobal; short fibers, woven and non-woven fabrics, used in health care products and in the agricultural and clothing fields.
Compared with the prior art, the invention has the beneficial effects that: the biodegradable polyester composition is good in biodegradability and excellent in mechanical property. More importantly, the biodegradable polyester composition of the invention is compostable at home according to the italian standard UNI11355: 2010.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the following examples, those not specifically described are commercially available. The melt index of the biodegradable polyester is determined according to ASTM D1238 using a weight of 2.16kg and a temperature of 190 ℃, the Total Organic Carbon (TOC) content of the biological filler and of the degradable bio-based masterbatch being measured according to ISO16620-2 standard. The particle size testing method of the biological filler in the degradable biological-based master batch in the embodiment comprises the following steps:
a) placing 2.0-3.0 g of the degradable bio-based master batch in a crucible;
b) placing the crucible filled with the degradable bio-based master batch in a muffle furnace, and firing for 30-45 minutes at 700 ℃;
c) the particle size of the residue after firing was measured according to the method of GB/T19077.1 "particle size analysis laser diffraction method".
In the following examples, PLA represents polylactic acid, PHA represents polyhydroxyalkanoate, PBS represents polybutylene succinate, PBSA represents polybutylene adipate-co-polybutylene succinate, PBAT represents polybutylene adipate-terephthalate, PBST represents polybutylene succinate-terephthalate, and PBSeT represents polybutylene sebacate-terephthalate.
Examples 1 to 7
The components of the degradable bio-based masterbatch of examples 1 to 7 are shown in table 1. The preparation method of the degradable bio-based master batch in the embodiment 1-7 comprises the following steps: uniformly mixing the components in the degradable bio-based master batch according to a proportion, putting the mixture into a double-screw extruder, extruding and granulating at 140-220 ℃ to obtain the degradable bio-based master batch.
The components of the biodegradable polyester compositions of examples 1 to 7 are shown in table 2, and the preparation methods of the biodegradable polyester compositions of examples 1 to 7 are as follows: uniformly mixing the components in the biodegradable polyester according to a certain proportion, putting the mixture into a single-screw film blowing machine, blowing the film at the temperature of 120-180 ℃, or putting the mixture into an extruder after uniformly mixing, extruding and granulating at the temperature of 140-220 ℃ to obtain the biodegradable polyester.
Meanwhile, the biodegradable polyester compositions of examples 1 to 7 were respectively prepared into 12 μm + -1 μm films, the longitudinal tear strength and the transverse tear strength thereof were tested according to the standard ASTM D-882/88, the biodegradation rate thereof after 12 weeks was tested according to the standard ISO 169929 (2013), and the test results are shown in Table 2.
Table 1 examples 1-7 degradable bio-based masterbatch
TABLE 2 examples 1 to 7 biodegradable polyester compositions
As can be seen from table 2, the biodegradable polyester composition prepared by using the biodegradable bio-based masterbatch of the present invention has excellent biodegradability and tear strength.
Effect example 1
The weight ratio of the biodegradable polyester to the biological filler in the degradable biological-based master batch of the invention can affect the biodegradation performance and the tearing strength of the biodegradable polyester composition containing the master batch. In order to examine the influence of the weight ratio of the biodegradable polyester to the biological filler on the biodegradability and tear strength of the biodegradable polyester composition, the following biodegradable polyester compositions of test groups 1 to 5 and control groups 1 to 4 were prepared in this effect example. The biodegradable polyester compositions of the test groups 1-5 and the control groups 1-4 comprise the following components in parts by weight: 50-90 parts of aliphatic polyester or aliphatic-aromatic copolyester, 0-35 parts of natural polymer, 5-40 parts of degradable bio-based master batch, 0-5 parts of inorganic filler and 0-4 parts of auxiliary agent; the degradable bio-based masterbatch comprising a biodegradable polyester and a bio-filler, the biodegradable polyester having a melt index of 8-80g/10min, the melt index of the biodegradable polyester being measured according to ASTM D1238 using a weight of 2.16kg and at a temperature of 190 ℃; the biological filler is from natural biomass resources, the total organic carbon in the biological filler accounts for more than 80 percent of the total carbon weight in the biological filler, and the particle size D of the biological filler500.5 to 8 μm; the weight ratio of the biodegradable polyester and the biological filler is shown in the following table 3, and the total organic carbon in the degradable bio-based master batch accounts for 60-100% of the total carbon in the degradable bio-based master batch. The biodegradable polyester compositions of test groups 1 to 5 and control groups 1 to 4 were all the same except that the weight ratio of the biodegradable polyester to the biological filler was different.
In this effect example, the biodegradable rates and tear strengths of the biodegradable polyester compositions of the test groups 1 to 5 and the control groups 1 to 4 were also measured according to the methods for testing the performance of the biodegradable polyester compositions of examples 1 to 7, and the test results are shown in table 3.
TABLE 3
As can be seen from table 3, when the weight ratio of the biodegradable polyester and the biological filler is within the range of the present invention, the biodegradable polyester composition obtained has better biodegradability and tear strength, especially when the weight ratio of the biodegradable polyester and the biological filler is 25 to 35: 65 to 75, the resulting polyester composition is particularly excellent in biodegradability and tear strength.
Effect example 2
The melt index of the biodegradable polyester in the degradable bio-based master batch of the invention can influence the biodegradation performance and the tearing strength of the biodegradable polyester composition containing the master batch. In order to examine the influence of the melt index of biodegradable polyester on the biodegradability and tear strength of the biodegradable polyester composition, the following biodegradable polyester compositions of test groups 1 to 7 and control groups 1 to 4 were prepared in this effect example. The biodegradable polyester compositions of the test groups 1-7 and the control groups 1-4 comprise the following components in parts by weight: 50-90 parts of aliphatic polyester or aliphatic-aromatic copolyester, 0-35 parts of natural polymer, 5-40 parts of degradable bio-based master batch, 0-5 parts of inorganic filler and 0-4 parts of auxiliary agent; the biodegradable bio-based master batch comprises biodegradable polyester and a biological filler, wherein the melt index of the biodegradable polyester is shown in Table 4, the biological filler is derived from natural biomass resources, total organic carbon in the biological filler accounts for more than 80% of the total carbon in the biological filler by weight, and the particle size D of the biological filler500.5 to 8 μm; the weight ratio of the biodegradable polyester to the biological filler is 20-40: 60-80 parts; the total organic carbon in the degradable bio-based master batch accounts for 60-100% of the weight of the total carbon in the degradable bio-based master batch. The biodegradable polyester compositions of test groups 1 to 7 and control groups 1 to 4 were all the same except that the melt index of the biodegradable polyester was different.
In this effect example, the biodegradation rate and the tear strength of the biodegradable polyester compositions of the test groups 1 to 7 and the control groups 1 to 4 were also measured according to the method for measuring the performance of the biodegradable polyester compositions of the examples 1 to 7, and the measurement results are shown in table 4.
TABLE 4
As can be seen from Table 4, when the melt index of the biodegradable polyester in the biodegradable bio-based masterbatch is 10-60g/10min, the biodegradability and the tear strength of the obtained biodegradable polyester composition are better, especially when the melt index is 15-45g/10min, the biodegradability and the tear strength of the obtained biodegradable polyester composition are best.
Effect example 3
The grain size of the biological filler in the degradable biological-based master batch influences the tearing strength of the biodegradable polyester composition containing the master batch. In order to examine the influence of the particle size of the bio-filler on the tear strength of the biodegradable polyester composition, the following biodegradable polyester compositions of test groups 1 to 7 and control groups 1 to 4 were prepared in this effect example. The biodegradable polyester compositions of the test groups 1-7 and the control groups 1-4 comprise the following components in parts by weight: 50-90 parts of aliphatic polyester or aliphatic-aromatic copolyester, 0-35 parts of natural polymer, 5-40 parts of degradable bio-based master batch, 0-5 parts of inorganic filler and 0-4 parts of auxiliary agent; the degradable bio-based masterbatch comprising a biodegradable polyester and a bio-filler, the biodegradable polyester having a melt index of 8-80g/10min, the melt index of the biodegradable polyester being measured according to ASTM D1238 using a weight of 2.16kg and at a temperature of 190 ℃; the biological filler is from natural biomass resources, the total organic carbon in the biological filler accounts for more than 80 percent of the total carbon weight in the biological filler, and the particle size D of the biological filler50As shown in table 5; the weight ratio of the biodegradable polyester to the biological filler is 20-40: 60-80 parts; the total organic carbon in the degradable bio-based master batch accounts for the degradable bio-based master batch60-100% of the total carbon weight.
The biodegradable polyester compositions of test groups 1 to 7 and control groups 1 to 4 were all the same except that the particle size of the biological filler was different.
In this effect example, the tear strength of the biodegradable polyester compositions of the test groups 1 to 7 and the control groups 1 to 4 was also measured according to the method for measuring the performance of the biodegradable polyester compositions of examples 1 to 7, and the measurement results are shown in table 5.
TABLE 5
As can be seen from Table 5, the particle size D of the biological filler in the degradable bio-based masterbatch is50When the particle size of the biological filler is 0.8-6 mu m, the obtained biodegradable polyester composition has better tearing strength, especially when the particle size D of the biological filler50The tear strength of the polyester composition is best when the thickness is 1 to 5 μm.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (11)
1. The degradable bio-based master batch is characterized by comprising biodegradable polyester and a biological filler, wherein the weight ratio of the biodegradable polyester to the biological filler is (20-40): 60-80 parts; the biological filler is from natural biomass resources, the total organic carbon in the biological filler accounts for more than 80 percent of the total carbon weight in the biological filler, and the particle size D of the biological filler500.5 to 8 μm;
the total organic carbon in the degradable bio-based master batch accounts for 60-100% of the weight of the total carbon in the degradable bio-based master batch; the biodegradable polyester has a melt index of 10 to 60g/10min, measured according to ASTM D1238 using a weight of 2.16kg and at a temperature of 190 ℃.
2. The degradable bio-based masterbatch according to claim 1, wherein the weight ratio of the biodegradable polyester to the bio-filler is 25-35: 65-75.
3. The degradable bio-based masterbatch according to claim 1 wherein said biodegradable polyester has a melt index of 15 to 45g/10min as measured according to ASTM D1238 using a weight of 2.16kg and at a temperature of 190 ℃.
4. The degradable bio-based masterbatch of claim 1 wherein the particle size D of said bio-filler is500.8 to 6 μm.
5. The degradable bio-based masterbatch of claim 4 wherein the bio-filler has a particle size D501 to 5 μm.
6. The degradable bio-based masterbatch according to any one of claims 1 to 5, wherein at least one of the following (a) to (b):
(a) the biodegradable polyester is at least one of polylactic acid, polyhydroxyalkanoate, polybutylene succinate, polybutylene adipate-co-polybutylene succinate, polybutylene adipate-terephthalate, polybutylene succinate-terephthalate and polybutylene sebacate-terephthalate;
(b) the biological filler is at least one of animal bone, eggshell, coral, shell, Concha Ostreae, and nacreous layer.
7. The preparation method of the degradable bio-based master batch according to any one of claims 1 to 6, comprising the following steps: uniformly mixing the components in the degradable bio-based master batch according to a proportion, putting the mixture into a double-screw extruder, extruding and granulating at 140-220 ℃ to obtain the degradable bio-based master batch.
8. The biodegradable polyester composition is characterized by comprising the following components in parts by weight: 50-90 parts of aliphatic polyester or aliphatic-aromatic copolyester, 0-35 parts of natural polymer, 5-40 parts of the degradable bio-based master batch of any one of claims 1-6, 0-5 parts of inorganic filler and 0-4 parts of auxiliary agent.
9. The biodegradable polyester composition according to claim 8, wherein at least one of the following (I) to (IV):
the aliphatic polyester is at least one of polybutylene succinate and polybutylene adipate-co-polybutylene succinate, and the aliphatic-aromatic copolymer is at least one of polybutylene adipate-co-terephthalate, polybutylene succinate-co-terephthalate and polybutylene sebacate-co-terephthalate;
(II) the polymer of natural origin is at least one of starch and polylactic acid;
(III) the inorganic filler is selected from at least one of talcum powder, montmorillonite, kaolin, graphite, gypsum, conductive carbon black, calcium chloride, ferric oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber and mineral fiber;
and (IV) the auxiliary agent is at least one of a plasticizer, a release agent, a surfactant, wax, an antistatic agent, a dye, a UV absorbent and a UV stabilizer.
10. The method for preparing the biodegradable polyester composition according to claim 9 or 8, comprising the steps of: uniformly mixing the components in the biodegradable polyester according to a certain proportion, putting the mixture into a single-screw film blowing machine, blowing the film at the temperature of 120-180 ℃, or putting the mixture into an extruder after uniformly mixing, extruding and granulating at the temperature of 140-220 ℃ to obtain the biodegradable polyester.
11. A film or film bag comprising the biodegradable polyester composition according to claim 9 or 8.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595857.7A CN109627709B (en) | 2018-12-25 | 2018-12-25 | Degradable bio-based master batch and preparation method and application thereof |
| PCT/CN2019/121836 WO2020134850A1 (en) | 2018-12-25 | 2019-11-29 | Degradable bio-based masterbatch and preparation method therefor and application thereof, |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595857.7A CN109627709B (en) | 2018-12-25 | 2018-12-25 | Degradable bio-based master batch and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109627709A CN109627709A (en) | 2019-04-16 |
| CN109627709B true CN109627709B (en) | 2021-04-27 |
Family
ID=66077571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811595857.7A Active CN109627709B (en) | 2018-12-25 | 2018-12-25 | Degradable bio-based master batch and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109627709B (en) |
| WO (1) | WO2020134850A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627709B (en) * | 2018-12-25 | 2021-04-27 | 金发科技股份有限公司 | Degradable bio-based master batch and preparation method and application thereof |
| CN110217894B (en) * | 2019-05-23 | 2021-12-14 | 北京博泰至淳生物科技有限公司 | Completely biodegradable slow-release solid carbon source capable of being directly put in and preparation method and application thereof |
| CN111410765B (en) * | 2020-03-26 | 2021-04-30 | 中山大学 | Preparation method of biodegradable polyester expanded bead and molded body material |
| CN112080114B (en) * | 2020-09-21 | 2024-04-16 | 天元军融(辽宁)化工研究所新材料孵化器股份有限公司 | Degradable plastic master batch and preparation method of degradable plastic |
| EP3991864A1 (en) * | 2020-10-29 | 2022-05-04 | Gaia Holding AB | Biodegradable and compostable composition for use as an agricultural film |
| CN112341767A (en) * | 2020-11-02 | 2021-02-09 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film for flue-cured tobacco planting and preparation method thereof |
| CN112390987A (en) * | 2020-11-16 | 2021-02-23 | 国网辽宁省电力有限公司辽阳供电公司 | Preparation method of deformable working tool based on high-molecular organic material |
| CN113354843B (en) * | 2020-12-23 | 2023-01-20 | 上海瞬吾商务咨询中心 | Preparation method and application of high-molecular degradable master batch |
| TWI768953B (en) * | 2021-06-04 | 2022-06-21 | 行政院農業委員會水產試驗所 | A film containing shell powder and application thereof |
| CN114196220A (en) * | 2021-12-27 | 2022-03-18 | 深圳百市达生物技术有限公司 | Preparation method of fully-degradable biomass fiber-based waterproof dinner plate |
| CN115386208A (en) * | 2022-08-11 | 2022-11-25 | 长兴电子（苏州）有限公司 | Degradable micro-bead and preparation method and application thereof |
| CN115746708A (en) * | 2022-12-10 | 2023-03-07 | 河北泽润工程橡塑有限公司 | Bio-based low-temperature-resistant spraying quick-setting rubber asphalt waterproof material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5667574A (en) * | 1996-11-06 | 1997-09-16 | Chi May Co., Ltd. | Starch-based composition for preparing an environment degradable α-olefinic polymer molding material |
| CN102516723A (en) * | 2011-12-12 | 2012-06-27 | 金发科技股份有限公司 | Filling masterbatch used in biodegradable plastic, and preparation method thereof |
| CN105504363A (en) * | 2016-01-07 | 2016-04-20 | 东莞市酬勤包装制品有限公司 | Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method |
| CN108219396A (en) * | 2017-12-27 | 2018-06-29 | 杨红梅 | A kind of biodegradable polymer blend and its application |
| CN108795001A (en) * | 2018-05-28 | 2018-11-13 | 金发科技股份有限公司 | A kind of biodegradable polymer composition and its application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028160A (en) * | 1998-10-01 | 2000-02-22 | Cortec Corporation | Biodegradable vapor corrosion inhibitor products |
| CN101805523B (en) * | 2010-04-06 | 2012-11-14 | 王文广 | Superfine biological powder filling masterbatch and method for preparing same |
| CN109627709B (en) * | 2018-12-25 | 2021-04-27 | 金发科技股份有限公司 | Degradable bio-based master batch and preparation method and application thereof |
-
2018
- 2018-12-25 CN CN201811595857.7A patent/CN109627709B/en active Active
-
2019
- 2019-11-29 WO PCT/CN2019/121836 patent/WO2020134850A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5667574A (en) * | 1996-11-06 | 1997-09-16 | Chi May Co., Ltd. | Starch-based composition for preparing an environment degradable α-olefinic polymer molding material |
| CN102516723A (en) * | 2011-12-12 | 2012-06-27 | 金发科技股份有限公司 | Filling masterbatch used in biodegradable plastic, and preparation method thereof |
| CN105504363A (en) * | 2016-01-07 | 2016-04-20 | 东莞市酬勤包装制品有限公司 | Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method |
| CN108219396A (en) * | 2017-12-27 | 2018-06-29 | 杨红梅 | A kind of biodegradable polymer blend and its application |
| CN108795001A (en) * | 2018-05-28 | 2018-11-13 | 金发科技股份有限公司 | A kind of biodegradable polymer composition and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020134850A1 (en) | 2020-07-02 |
| CN109627709A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627709B (en) | Degradable bio-based master batch and preparation method and application thereof | |
| EP2586821B1 (en) | Degradable starch-based plastic masterbatch and preparation method thereof | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| KR101477049B1 (en) | Novel biodegradable polymer composition useful for the preparation of biodegradable plastic and a process for the preparation of said composition | |
| Yu et al. | Polymer blends and composites from renewable resources | |
| CN102277005B (en) | Highly-filled fully-biodegradable packaging material | |
| Popa et al. | Polyhydroxybutyrate blends: A solution for biodegradable packaging? | |
| CN103289134B (en) | Multifunctional ground-covering film of fully biodegradable and preparation method thereof | |
| CN113652063A (en) | Calcium carbonate filled PBAT/PLA degradable film and preparation method thereof | |
| CN101649072B (en) | Full-degradable biological material and film product thereof | |
| MXPA06007104A (en) | Polymer blends with improved rheology and improved unnotched impact strength. | |
| CN101792591A (en) | Full-biodegradable plastic film and preparation method thereof | |
| CN112029154A (en) | Biodegradable material and preparation method thereof | |
| CN113956640B (en) | Biodegradable PLA film and preparation method thereof | |
| CN103756270A (en) | Full biodegrade mulch master batch as well as preparation method and application thereof | |
| CN114729165A (en) | Biodegradable resin composition and method for producing same | |
| US11952489B2 (en) | Biologically degradable film | |
| CA3058958C (en) | Biodegradable film | |
| Kanabenja et al. | 3D printing filaments from plasticized Polyhydroxybutyrate/Polylactic acid blends reinforced with hydroxyapatite | |
| CN104945870A (en) | All-biodegradable modified polylactic acid film-blowing resin and preparation method thereof | |
| CN114933815A (en) | Straw composite material master batch and preparation method thereof | |
| CN103183937B (en) | A kind of modified polylactic acid composite material and preparation method thereof | |
| CN102424719B (en) | Straw powder-containing modified poly lactic acid composite material and preparation method thereof | |
| JP2024012074A (en) | Tea fiber/phbv/pbat ternary composite, and preparation method and application thereof | |
| CN114836012A (en) | Completely biodegradable garbage bag film material and preparation method of garbage bag film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |