CN113429754A - Composite filled fully-degradable material composition, film and preparation method thereof - Google Patents
Composite filled fully-degradable material composition, film and preparation method thereof Download PDFInfo
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- CN113429754A CN113429754A CN202110728644.2A CN202110728644A CN113429754A CN 113429754 A CN113429754 A CN 113429754A CN 202110728644 A CN202110728644 A CN 202110728644A CN 113429754 A CN113429754 A CN 113429754A
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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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- 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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention belongs to the field of material degradation, and discloses a composite filled fully-degradable material composition, a film and a preparation method thereof. The composition comprises the following raw materials in parts by weight: 40-90 parts of PBAT, 5-20 parts of PLA, 10-30 parts of organic filler, 5-20 parts of inorganic filler, 1-15 parts of plasticizer, 0.3-1 part of coupling agent, 0.3-1 part of compatilizer, 0.3-1 part of lubricant and 0.2-1 part of compatibilizer. The material provided by the invention has the advantages of simple processing method, easy equipment operation and lower preparation cost of the product. The film prepared by the invention has good mechanical property, is low in price and has great commercial value in the field of plastic packaging.
Description
Technical Field
The invention relates to the field of full degradation, in particular to a composite filled full degradation material composition, a film and a preparation method thereof.
Background
Since the traditional plastic products (polyethylene, polypropylene, etc.) come out, the traditional plastic products have penetrated into all aspects of our lives, and the traditional plastic products bring convenience to our lives and simultaneously continuously present serious challenges to our living environment. Therefore, it is an urgent task to prepare a class of materials that can be completely degraded.
The poly (butylene adipate terephthalate) (PBAT) and the poly (lactic acid) (PLA) are two kinds of fully degradable materials which are the hottest in the market at present, and the fully degradable materials prepared by blending the two materials have the characteristics of the two materials and show good strength and elongation at break. But the poor compatibility and high price between PBAT and PLA severely limit their practical applications.
Disclosure of Invention
The invention aims to overcome the problems of poor compatibility between PBAT/PLA and fillers and high price of a fully degradable material prepared from the PBAT/PLA in the prior art, and provides a composite filled fully degradable material composition, a film and a preparation method thereof. The film prepared from the composition provided by the invention has the advantages of low price, good compatibility among components and excellent performance.
In order to achieve the above object, in a first aspect of the present invention, there is provided a composite filled fully degradable material composition, which comprises the following raw materials in parts by weight:
PBAT40-90 parts by weight, PLA5-20 parts by weight, organic filler 10-30 parts by weight, inorganic filler 5-20 parts by weight, plasticizer 1-15 parts by weight, coupling agent 0.3-1 part by weight, compatilizer 0.3-1 part by weight, lubricant 0.3-1 part by weight, and compatibilizer 0.2-1 part by weight.
In a second aspect, the invention provides a preparation method of a composite filled fully degradable film, which is prepared by using the composition of the invention, and the preparation method comprises the following steps:
(1) uniformly mixing the organic filler and the plasticizer in proportion to obtain a material A;
(2) uniformly mixing the inorganic filler and the coupling agent in proportion to obtain a material B;
(3) uniformly mixing PBAT, PLA, a compatilizer, a lubricant and a compatibilizer with the material A and the material B in proportion to obtain a mixed material;
(4) putting the mixed material into a double-screw extruder, and extruding and granulating to obtain modified particles;
(5) and putting the modified particles into a blow molding machine, and carrying out blow molding to obtain the composite filled fully-degradable film.
Compared with the prior art, the invention has the following beneficial effects:
(1) good compatibility between PBAT/PLA and the filler is realized;
(2) the cost is reduced by adding the filler;
(3) the economic benefit is realized while the environmental protection problem is solved.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a composite filled fully degradable material composition, which comprises the following raw materials in parts by weight:
PBAT40-90 parts by weight, PLA5-20 parts by weight, organic filler 10-30 parts by weight, inorganic filler 5-20 parts by weight, plasticizer 1-15 parts by weight, coupling agent 0.3-1 part by weight, compatilizer 0.3-1 part by weight, lubricant 0.3-1 part by weight, and compatibilizer 0.2-1 part by weight.
According to the invention, the PBAT, the PLA, the starch and the inorganic filler are blended, the compatilizer and the coupling agent are added, so that the compatibility among materials can be increased, and the compatilizer is introduced to further increase the compatibility among the PBAT/PLA/starch and the molecular weight of the polyester, so that the prepared fully-degradable film is low in price, keeps good performance and has strong market competitiveness.
In the present invention, preferably, the composition comprises the following raw materials in parts by weight:
PBAT60-90 parts by weight, PLA10-20 parts by weight, organic filler 15-30 parts by weight, inorganic filler 10-20 parts by weight, plasticizer 5-15 parts by weight, coupling agent 0.5-0.8 part by weight, compatilizer 0.5-0.8 part by weight, lubricant 0.5-1 part by weight, and compatibilizer 0.5-1 part by weight.
In the present invention, preferably, the weight average molecular weight of the polybutylene adipate terephthalate (PBAT) is 40000-200000.
In the present invention, preferably, the polylactic acid (PLA) has a weight average molecular weight of 40000-300000.
In order to further reduce the cost and increase the degradation performance of the material, plant extracts are adopted in the invention, and the sources of the plant extracts are wide and the prices are low, such as plant extracted starch. In the present invention, preferably, the organic filler is at least one or more of wheat starch, tapioca starch, corn starch and potato starch.
In order to further satisfy the requirements of harmless and environmental protection, in the present invention, it is preferable that the inorganic filler is at least one or more of calcium carbonate, barium sulfate, talc, montmorillonite, kaolin, silica and clay.
In the present invention, preferably, the plasticizer is at least one or more of water, glycerin, diethanolamine, triethanolamine, diglycerin, diethylene glycol, ethylene glycol, sorbitol, and urea.
In the present invention, preferably, the coupling agent is at least one or more of a titanate coupling agent, an aluminate coupling agent, a silane coupling agent, and a titanate-aluminate composite coupling agent. By adding the coupling agent, the interfacial interaction between the inorganic filler and the polyester resin is further increased, so that the compatibility is increased.
In the present invention, preferably, the compatibilizer is at least one or more of succinic acid, pyromellitic anhydride, citric acid, tributyl citrate, tartaric acid, and maleic anhydride.
In the present invention, preferably, the lubricant is at least one or more of triglycerol monostearate, erucamide, liquid paraffin, polyethylene wax, oxidized polyethylene wax, oleamide, and pentaerythritol stearate.
In the present invention, preferably, the compatibilizer is
Glycidyl methacrylateAnd at least one or more of epoxy styrene-acrylic copolymers. By adding the compatibilizer, the molecular weight of the polyester is further improved, and the compatibility and viscosity of the system are increased.
In a second aspect, the invention provides a preparation method of a composite filled fully degradable film, which adopts the composition to prepare, and the preparation method comprises the following steps:
(1) uniformly mixing the organic filler and the plasticizer in proportion to obtain a material A;
(2) uniformly mixing the inorganic filler and the coupling agent in proportion to obtain a material B;
(3) uniformly mixing PBAT, PLA, a compatilizer, a lubricant and a compatibilizer with the material A and the material B in proportion to obtain a mixed material;
(4) putting the mixed material into a double-screw extruder, and extruding and granulating to obtain modified particles;
(5) and putting the modified particles into a blow molding machine, and carrying out blow molding to obtain the composite filled fully-degradable film.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, corn starch 20 weight parts, calcium carbonate 10 weight parts, glycerol 10 weight parts, water 1 weight part, silane coupling agent 0.5 weight part, tributyl citrate 0.5 weight part, oleamide 0.6 weight part,
0.6 part by weight.
Example 2
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, corn starch 20 weight parts, talcum powder 10 weight parts, glycerol 10 weight parts, silane coupling agent 0.5 weight parts, maleic anhydride 0.5 weight parts, and erucamide 0 weight parts.6 parts by weight of a reaction product of (B),
0.6 part by weight.
Example 3
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, corn starch 20 weight parts, montmorillonite 10 weight parts, glycerol 10 weight parts, silane coupling agent 0.5 weight parts, citric acid 0.6 weight parts, erucamide 0.8 weight parts, and glycidyl methacrylate 0.5 weight parts.
Example 4
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, potato starch 20 weight parts, talcum powder 10 weight parts, glycerol 10 weight parts, aluminate coupling agent 0.5 weight parts, tributyl citrate 0.6 weight parts, erucamide 0.8 weight parts,
0.5 part by weight.
Example 5
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, potato starch 20 weight parts, calcium carbonate 10 weight parts, sorbitol 5 weight parts, glycerol 5 weight parts, titanate-aluminate composite coupling agent 0.5 weight parts, citric acid 0.6 weight parts, erucic amide 0.8 weight parts,
0.5 part by weight.
Example 6
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, potato starch 20 weight parts, montmorillonite 10 weight parts, sorbitol 5 weight parts, glycerol 5 weight parts, silane coupling agent 0.5 weight parts, citric acid 0.6 weight parts, erucic amide 0.8 weight parts,
0.5 part by weight.
Comparative example 1
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, corn starch 30 weight parts, glycerin 10 weight parts, water 1 weight part, tributyl citrate 0.5 weight part, oleamide 0.6 weight part,
0.6 part by weight.
Comparative example 2
A composite filled fully degradable material composition comprising:
PBAT70 weight parts, PLA10 weight parts, talcum powder 30 weight parts, silane coupling agent 1 weight part, tributyl citrate 0.5 weight part, oleamide 0.8 weight part,
0.6 part by weight.
Comparative example 3
A composite filled fully degradable material composition comprising:
PBAT88 weight parts, PLA12 weight parts, tributyl citrate 0.5 weight parts, oleamide 0.5 weight parts,
0.6 part by weight.
Preparation example
The above examples 1 to 6 and comparative examples 1 to 3 were prepared according to the following procedures to obtain films S1 to S6 and D1 to D3:
(1) uniformly blending the organic filler and the plasticizer in proportion, and obtaining a material A at the temperature of 50 ℃ for 20 min;
(2) uniformly blending the inorganic filler and the coupling agent in proportion, and obtaining a material B at normal temperature for 5 min;
(3) uniformly mixing PBAT, PLA, a compatilizer, a lubricant and a compatibilizer with the material A and the material B in proportion, and obtaining a mixed material at normal temperature for 5 min;
(4) and putting the mixed material into a double-screw extruder for extrusion, controlling the temperature at 50-200 ℃, and performing extrusion granulation to obtain modified particles. The specific temperature of each temperature zone is 70 ℃ in the first zone, 85 ℃ in the second zone, 130 ℃ in the third zone, 140 ℃ in the fourth zone, 150 ℃ in the fifth zone, 150 ℃ in the sixth zone, 150 ℃ in the seventh zone, 155 ℃ in the eighth zone, 157 ℃ in the ninth zone, 158 ℃ in the tenth zone, 160 ℃ in the eleventh zone, 160 ℃ in the twelfth zone, 160 ℃ in the thirteenth zone, and 160 ℃ at the head temperature of 160 ℃;
(5) and (3) putting the modified particles into a blow molding machine, controlling the temperature at 100-200 ℃, and performing blow molding to obtain the fully-degradable film. The specific temperature of each temperature zone is 135 ℃ in the first zone, 138 ℃ in the second zone, 140 ℃ in the third zone, 150 ℃ in the fourth zone, 150 ℃ in the fifth zone, 155 ℃ in the sixth zone, 160 ℃ in the seventh zone and 165 ℃ in the head.
Test example
The fully biodegradable particles and the film bags S1-S6 and D1-D3 prepared above were tested, and the test results are shown in Table 1 below.
Performance evaluation method:
the fully degradable plastic bags prepared by the above method were subjected to the following tests.
The lifting test, the drop test and the water leakage test are carried out according to the national standard GBT 38082-2019;
the dart drop impact test was performed according to GB/T9639.1-2008;
the heat seal strength test was performed according to QB/T2358.
TABLE 1
As can be seen from table 1, although D3 has the best performance, the product is unfilled, costly, and not commercially competitive. The fully-degradable plastic bag prepared by the composite filling strategy provided by the invention not only shows excellent performance and fully meets the national standard, but also has lower cost and higher commercial value in the field of plastic packaging products.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. The composite filled fully degradable material composition is characterized by comprising the following raw materials in parts by weight:
40-90 parts of PBAT, 5-20 parts of PLA, 10-30 parts of organic filler, 5-20 parts of inorganic filler, 1-15 parts of plasticizer, 0.3-1 part of coupling agent, 0.3-1 part of compatilizer, 0.3-1 part of lubricant and 0.2-1 part of compatibilizer.
2. The composite filled fully degradable material composition according to claim 1 wherein the composition comprises the following raw materials in parts by weight:
60-90 parts of PBAT, 10-20 parts of PLA, 15-30 parts of organic filler, 10-20 parts of inorganic filler, 5-15 parts of plasticizer, 0.5-0.8 part of coupling agent, 0.5-0.8 part of compatilizer, 0.5-1 part of lubricant and 0.5-1 part of compatibilizer.
3. The composite filled fully degradable material composition according to claim 1 wherein the weight average molecular weight of the polybutylene adipate-terephthalate is 40000-200000.
4. The composite filled fully degradable material composition of claim 1 wherein the weight average molecular weight of the polylactic acid is 40000-300000.
5. The composite filled fully degradable material composition of claim 1 wherein the organic filler is at least one or more of wheat starch, tapioca starch, corn starch and potato starch.
6. The composite filled fully degradable material composition of claim 1 wherein the inorganic filler is at least one or more of calcium carbonate, barium sulfate, talc, montmorillonite, kaolin, silica and clay.
7. The composite filled fully degradable material composition of claim 1 wherein the plasticizer is at least one or more of water, glycerol, diethanolamine, triethanolamine, diglycerol and diethylene glycol, ethylene glycol, sorbitol and urea.
8. The composite filled fully degradable material composition of claim 1 wherein the coupling agent is at least one or more of a titanate coupling agent, an aluminate coupling agent, a silane coupling agent and a titanate-aluminate composite coupling agent.
9. The composite filled fully degradable material composition of claim 1 wherein the compatibilizer is at least one or more of succinic acid, pyromellitic anhydride, citric acid, tributyl citrate, tartaric acid, and maleic anhydride.
10. The composite filled fully degradable material composition of claim 1 wherein the lubricant is at least one or more of triglycerol monostearate, erucamide, liquid paraffin, polyethylene wax, oxidized polyethylene wax, oleamide and pentaerythritol stearate.
11. The composite filled fully degradable material composition of claim 1 wherein the compatibilizer is
At least one or more of glycidyl methacrylate and epoxy styrene-acrylic copolymer.
12. A method for preparing a composite filled fully degradable film, which is prepared by using the composition of any one of claims 1 to 11, the method comprising:
(1) uniformly mixing the organic filler and the plasticizer in proportion to obtain a material A;
(2) uniformly mixing the inorganic filler and the coupling agent in proportion to obtain a material B;
(3) uniformly mixing PBAT, PLA, a compatilizer, a lubricant and a compatibilizer with the material A and the material B in proportion to obtain a mixed material;
(4) putting the mixed material into a double-screw extruder, and extruding and granulating to obtain modified particles;
(5) and putting the modified particles into a blow molding machine, and carrying out blow molding to obtain the composite filled fully-degradable film.
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Cited By (4)
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| CN113773558A (en) * | 2021-10-21 | 2021-12-10 | 浙江绿禾生态科技股份有限公司 | PLA (polylactic acid), PBAT (poly (butylene adipate terephthalate) and ST (styrene terephthalate)) degradable composite material and production process thereof |
| CN114369346A (en) * | 2021-11-30 | 2022-04-19 | 苏州星火丰盈环保包装有限公司 | Biodegradable plastic garbage bag and preparation method thereof |
| CN115746350A (en) * | 2022-10-27 | 2023-03-07 | 江苏苏能新材料科技有限公司 | Preparation method of low-moisture-permeability fully-degradable agricultural film special material |
| WO2023056534A1 (en) * | 2021-10-07 | 2023-04-13 | Lam'on Ltd | Multilayer biodegradable film obtained by reactive co-extrusion |
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Application publication date: 20210924 |