CN117209989A - Ternary carbon dioxide-based copolymer degradable flexible film material and preparation method thereof - Google Patents
Ternary carbon dioxide-based copolymer degradable flexible film material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 13
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- 238000002844 melting Methods 0.000 claims description 7
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- 238000005520 cutting process Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001718 carbodiimides Chemical group 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 229920006125 amorphous polymer Polymers 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
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- QXZMTDQINLTPAX-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.C1(OCC(C)O1)=O Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.C1(OCC(C)O1)=O QXZMTDQINLTPAX-UHFFFAOYSA-N 0.000 description 1
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- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a PPCP degradable flexible film material, which is mainly prepared from the following raw materials: the anti-ultraviolet agent comprises PPCP, PPC and PBAT, a plasticizer, a chain extender, an antioxidant, an opening agent, an anti-hydrolysis agent and an anti-ultraviolet agent, wherein the mass part of the PPCP is 100, and the mass part of the PPC and the PBAT is 3-30. The film adopts PPC, PBAT and an auxiliary agent to modify PPCP, and the product has good ductility and elongation at break. The invention also discloses a preparation method of the PPCP degradable flexible film material.
Description
Technical Field
The invention belongs to the technical field of material modification, and particularly relates to a ternary carbon dioxide based copolymer (PPCP) degradable flexible film material and a preparation method thereof.
Background
Carbon dioxide (CO) 2 ) The copolymer of the Polypropylene Oxide (PO) and the polymethyl ethylene carbonate (PPC) is an environment-friendly plastic which can be completely degraded, and the PPC has excellent barrier property, chemical stability and electrical insulation property, and simultaneously has excellent flexibility, and the elongation at break can exceed 1000 percent. However, PPC belongs to an amorphous polymer, the acting force between molecular chains is small, the main chain segment is easy to rotate inwards around an ether bond (-O-) obtained by continuous insertion of PO, the glass transition temperature is low (about 35 ℃), the thermal stability is poor, and the use temperature and the application range of PPC are greatly limited. Many modification studies have been conducted to improve the thermodynamic properties of PPC to meet the demands of production processing applications. In recent years, the team was taught by university of Zhongshan Meng Yuezhong at CO 2 Based on PO monomer, phthalic Anhydride (PA) is introduced as a third monomer to modify PPC to obtain multiblock ternaryThe carbon dioxide copolymer PPCP (Poly (propylene carbonate phthalate)) has made breakthrough progress. The defects of the maximum thermodynamic performance of PPC are improved when the rigid groups of benzene rings are introduced, the tensile strength of the polymer can be improved to be more than 40Mpa, and the highest glass transition temperature can be more than 50 ℃, wherein the higher the PA content is, the higher the glass transition temperature of the polymer strength is. Compared with PPC, the ternary copolymer PPCP has higher strength and better thermal stability, and the comprehensive performance of the ternary copolymer PPCP is comparable with that of PLA, thus being hopeful to become a substitute of PLA. The PPCP is the most promising direction as the degradable plastic on disposable products, but the elongation at break of the PPCP is extremely low and is only about 5%, so that the application of the PPCP in the disposable flexible general plastic consumer markets such as shopping bags, packaging films, mulching films and the like is greatly limited, and the processing performance and the mechanical performance of the PPCP are improved, thereby being beneficial to promoting the development of PPCP products and the progress of the whole industry.
Disclosure of Invention
The invention aims to provide a PPCP plastic modification scheme, which is characterized in that PPCP is an aromatic polyester-aliphatic polycarbonate copolymer, and is modified by adopting an environment-friendly aromatic polybutylene terephthalate-adipic acid copolymer (PBAT), a flexible aliphatic polycarbonate (PPC) and a small amount of environment-friendly auxiliary agents by taking polymer compatibility into consideration and taking the PPCP as a polymer matrix.
The invention also aims to provide a preparation method of the PPCP degradable flexible film material.
The first object of the present invention can be achieved by the following technical means: the PPCP degradable flexible film material is mainly prepared from the following raw materials in parts by mass:
PPC is an environment-friendly plastic which can be completely degraded, has excellent barrier property, chemical stability and electrical insulation property, and has excellent flexibility, but PPC belongs to an amorphous polymer, and has small acting force among molecular chains, low glass transition temperature and poor thermal stability. The PBAT belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and polybutylene terephthalate, has the characteristics of PBA and PBT, has better ductility and elongation at break, has better toughness, is close to polyethylene PE, and has better heat resistance and impact property. The toughness of the PPCP material can be obviously improved by adding the ductile materials PPC and PBAT. The PPC and the PBAT belong to biodegradable plastics, so that the environmental friendliness of the whole composite material is not affected.
However, the solubility difference between PPC and PBAT is large, the former is amorphous polymer, and the latter is partially crystalline polymer, and the compatibility is poor. Unexpectedly, adding PPC and PBAT to PPCP can improve compatibility between PPC and PBAT.
Therefore, when the PPCP is modified, the PPC and a small amount of PBAT are added for modification, under the action of an antioxidant, a plasticizer and a chain extender, the PPC and the PBAT can improve the tensile property and the thermal stability of the PPCP, the problem of poor opening property of the PPCP can be solved by adding the opening agent, and other additives such as an anti-hydrolysis agent and an anti-aging agent are added, so that the PPCP modified plastic degradable film with excellent comprehensive performance is prepared.
In the invention, commercial PPC and PBAT are added into PPCP, and the PPCP/PPC/PBAT film is prepared by double-screw melt blending, and in the preparation process, in order to further improve the biocompatibility, ultraviolet resistance, oxidation resistance and stability of PPCP, PPC, PBAT, plasticizer oxo soybean oil (ESO), a chain extender ADR4468, plasticizer acetyl tributyl citrate (ATBC), an antioxidant AT1010, an antioxidant AT168 and an ultraviolet resistant agent UV-531 are added into the mixed material.
As a preferred embodiment of the invention, the PPCP degradable flexible film material comprises the following raw materials in parts by mass:
preferably, the plasticizer of the present invention is acetyl tributyl citrate (ATBC).
Preferably, the chain extender of the present invention is ADR-4468.PPCP, PPC, PBAT and the epoxy chain extender are subjected to ring-opening addition reaction, the tensile strength of the PPCP can be obviously increased by adding the chain extender, the higher tensile property is shown, and the thermal stability of the PPCP, PPC, PBAT composite system can be improved by adding the chain extender.
Preferably, the antioxidant is antioxidant 1010.
Preferably, the opening agent is silicon dioxide or talcum powder.
Preferably, the anti-hydrolysis agent of the present invention is a carbodiimide or an epoxy compound.
Preferably, the anti-ultraviolet agent is an ultraviolet absorber UV-531.
The second object of the present invention can be achieved by the following technical means: the preparation method of the PPCP degradable flexible film material comprises the following steps:
(1) Selecting raw materials PPCP, PPC and PBAT, and uniformly mixing a plasticizer, a chain extender, an antioxidant, an opening agent, an anti-hydrolysis agent and an anti-ultraviolet agent;
(2) Feeding the mixed raw materials into a homodromous parallel double-screw extruder for melting, homogenizing, extruding, cutting and granulating;
(3) And (5) film blowing by a film blowing machine to obtain the PPCP degradable flexible film material.
Preferably, the raw materials PPCP, PPC and PBAT in the step (1) are dried in a blast oven at 60 ℃ for 8 hours, and a countercurrent mixer is adopted for mixing.
Preferably, in the step (2), the temperature of the equidirectional parallel double-screw extruder is raised to 160-170 ℃, then materials are added, and the rotating speed of the main screw is regulated to be raised to 30-50 r/min.
When the film blowing machine is used for blowing the film at a proper temperature in the step (3), the proper temperature is set, heating is started, then the material particles are poured into a hopper, and the rotating speed, the traction speed and the winding speed of the screw are set for blowing the film.
Preferably, in the step (3), film blowing is performed at 130-145 ℃ by using a film blowing and casting integrated machine, the rotating speed of a screw is 15-25 rpm, the traction ratio is 1:1.15, and the traction ratio can be adjusted on the basis of the proportion.
Because the temperature of each section of the film blowing machine influences each index of the film, the temperature is set lower at the inlet of the feeding section, and the blocking of the feed inlet due to the sticking flow of resin is prevented; the temperature of the melting section needs to reach the viscous flow temperature; the temperature of the homogenization section and the melting section tail remained stable or slightly increased. Therefore, the invention adjusts the temperature of the feeding section of the film blowing and casting integrated machine to 130 ℃, the temperature of the melting section to 140 ℃ and the temperature of the homogenizing section to 145 ℃, and can achieve better film blowing effect.
The invention has the following advantages:
(1) According to the invention, the PPCP is modified by the PPC and the PBAT, so that the compatibility of the PPCP, the PPC and the PBAT is good, the flexibility of the PPCP can be effectively improved, and finally, the product with good comprehensive performance is obtained.
(2) When the PPC and the PBAT are adopted to modify the PPCP, the chain extender and the opening agent are added, so that the mechanical property and the technological property can be improved, and the opening property of the film can be improved; the plasticizer is added to enhance the flexibility and facilitate the processing; the antioxidant is added to protect the materials from thermooxidative degradation, so that the thermal stability is improved; the addition of the anti-ultraviolet agent has the maximum protection effect on the polymer, is beneficial to reducing the color and the luster, and simultaneously delays yellowing and delays the loss of physical properties; the addition of the hydrolysis resistance agent can improve the hydrolysis resistance of the polymer, increase the viscosity and strength and improve the processing stability.
(3) The PPCP degradable flexible film material has good flexibility, elongation at break, heat resistance and biodegradability.
(4) The PPCP degradable flexible film material and the preparation method thereof can well improve the compatibility among PPC, PBAT and PPCP, and the obtained modified product can be used for preparing the degradable flexible film material, and the PPCP degradable flexible film material can be widely applied to the fields of mulching films, shopping bags, garbage bags, food packaging bags and the like.
(5) Before film blowing, the invention needs to carry out double-screw extrusion granulation, so that all raw materials are plasticized uniformly; different from the prior art, the plastic is prepared by directly mixing materials uniformly and then adding the materials into a film blowing machine for film blowing.
Drawings
FIG. 1 is an external view picture of the PPCP degradable flexible film material prepared in examples 1-4 of the present invention;
fig. 2 is an SEM (electron microscopy) of the PPCP degradable flexible film material prepared in examples 1-4 of the present invention.
Detailed Description
PPC is from the crown of the river; PBAT is from zhuhai wantong chemical C1200; the raw materials adopted below are all commercial products unless specified.
First-part PPCP degradable flexible film material and preparation method thereof
Example 1
The PPCP degradable flexible film material provided by the embodiment is mainly prepared from the following raw materials in parts by mass:
the plasticizer is acetyl tributyl citrate (ATBC);
the chain extender is ADR-4468;
the antioxidant is antioxidant 1010;
the opening agent is talcum powder;
the hydrolysis resisting agent is carbodiimide;
the anti-ultraviolet agent is ultraviolet absorbent UV-531.
The preparation method of the PPCP degradable flexible film material comprises the following steps:
(1) Selecting raw materials PPCP, PPC and PBAT, and uniformly mixing a plasticizer, a chain extender, an antioxidant, an opening agent, an anti-hydrolysis agent and an anti-ultraviolet agent;
(2) Plasticizing and granulating by adopting a homodromous parallel double-screw extruder, adjusting the temperature to melt and homogenize the mixed raw materials, and cutting and granulating by using a granulator;
(3) And (5) blowing the film at a proper temperature by using a film blowing machine to obtain the PPCP degradable flexible film.
And (3) drying the raw materials PPCP, PPC and PBAT in a blast oven at 60 ℃ for 8 hours, and mixing by using a countercurrent mixer.
In the step (2), plasticizing and granulating comprises the steps of confirming that a hopper, a feeding port and a die head of a parallel double-screw extruder are clean, starting up, setting processing temperature, selectively heating to 170 ℃, adding materials, regulating the rotating speed of a main screw to gradually rise to 40r/min, and then opening the feeding port and the die head to extrude wires into cooling water to be granulated and collected in the granulator.
In the step (3), a film blowing and casting integrated machine is used for blowing films at a proper temperature, the temperature of a feeding section is adjusted to 125 ℃, the temperature of a melting section is adjusted to 130 ℃, the temperature of a homogenizing section is adjusted to 135 ℃, heating is started, material particles are poured into a hopper, the rotating speed of a screw is set to 20rpm, and the speed ratio of a traction speed to a winding speed is 1:1.1, wherein the traction speed is 0.6rpm, the winding speed is 0.7rpm, clicking is started, the speed is adjusted according to the requirement, and after the experiment is finished, 500g of washing machine material is added for washing the machine.
The prepared PPCP degradable flexible film material is shown in figure 1 (a). It can be seen from fig. 1 (a) that the PPCP-modified plastic degradable film is relatively uniform. SEM image as shown in fig. 2 (a), the PPCP modified degradable film had some wrinkles and slightly uneven film thickness.
Example 2
Unlike example 1, the parts by weight of PPC and PBAT were 10 and 20.
The prepared PPCP degradable flexible film material is shown in fig. 1 (b), the polymer film is uniform, the scanning electron microscope image is shown in fig. 2 (b), and as can be seen from fig. 2, compared with fig. 1 in example 1, the section of the PPCP modified plastic film has no obvious phase separation.
Example 3
Unlike example 1, the parts by weight of PPC and PBAT were 20 and 10.
The prepared PPCP degradable flexible film material is shown in the figure 1 (c), the polymer is relatively uniform, the scanning electron microscope image is shown in the figure 2 (c), the prepared PPCP degradable flexible film material has good compatibility, and small particles are formed, but are invisible to naked eyes and do not affect the use.
Example 4
Unlike example 1, the parts by weight of PPC and PBAT were 25 and 5.
The prepared PPCP degradable flexible film material is shown in a figure 1 (d), the polymer is relatively uniform, a scanning electron microscope image is shown in a figure 2 (d), the prepared PPCP degradable flexible film material has relatively good compatibility, but a small amount of island structures appear.
Comparative example 1
Unlike example 2, the film-forming material consisted of PPCP and PPC, the mass ratio of PPC was 20, no PBAT was added, other auxiliaries and the preparation method were the same as in example 1.
Comparative example 2
Unlike example 2, the film-forming material consisted of PPCP and PBAT, the weight fraction of PBAT was 20, PPC was not added, and other auxiliaries and preparation method were the same as in example 1.
Comparative example 3
Unlike example 2, no plasticizer was added.
Comparative example 3
Unlike example 2, no opening agent was added.
Comparative example 4
Unlike example 2, the materials were directly mixed without pelletization and then blown to prepare the film.
Second part examples 1-4 and comparative examples 1-5 Performance test of films prepared
2.1 test methods
Mechanical properties: and testing by using a GBH electronic tensile tester according to the method of national standard ISO1184-1983, selecting a sample with uniform and even thickness, and cutting out a film sample with the length of 100mm and the width of 10 mm. Setting the speed of a stretcher to be 50mm/min, carrying out vertical stretching test on the film, and obtaining the mechanical property data of the prepared film according to the experiment. Repeating for 3 times, carrying out corresponding mechanical property measurement, recording the tensile strength and the breaking elongation of the sample film, and taking data average value when calculating the mechanical property to obtain a final result.
2.2 test results
The PPCP degradable flexible film materials prepared in examples 1-4 and the films prepared in comparative examples 1-4 were tested for tensile strength and elongation at break, and the results are shown in Table 1 below.
TABLE 1 comparison of the Properties of the films of examples 1-4 and comparative examples 1-5
| Examples | Tensile strength (MPa) | Elongation at break (%) |
| Example 1 | 18.3±1.42 | 517.6±36.9 |
| Example 2 | 16.3±0.35 | 560.8±82.6 |
| Example 3 | 15.5±0.56 | 489.2±42.4 |
| Example 4 | 13.6±0.87 | 421.2±61.1 |
| Comparative example 1 | 11.7±0.90 | 592.5±19.4 |
| Comparative example 2 | 13.3±0.47 | 255.45±62.1 |
| Comparative example 3 | 10.2±1.56 | 259.6±87.4 |
| Comparative example 4 | 8.4±1.13 | 10.2±4.5 |
From Table 1, comparison of examples 1-4 with comparative examples 1-4 shows that:
(1) From the data in Table 1, it can be seen that in example 2, the flexibility of the modified material was optimal when the PPC and PBAT were 10 and 20 parts by mass;
(2) Comparative example 1 resulted in a decrease in tensile strength of the product due to the absence of PBAT as compared to example 2;
(3) Comparative example 2 has reduced elongation at break of the product due to the lack of PPC compared to example 2;
(4) Compared with example 2, comparative example 3 does not add plasticizer, so that the tensile strength and elongation at break of the product are obviously reduced, and particularly, the elongation at break is obviously reduced;
(5) In contrast to example 2, comparative example 5 did not carry out pelletization, but the material was directly blown into a film, and the elongation at break and tensile strength were much lower than those of example 2.
Therefore, the optimal formula of the invention is to modify PPCP by PPC and PBAT, and the optimal PPCP degradable flexible film material formula is obtained under the action of auxiliary agents such as plasticizer, chain extender, antioxidant, opening agent and the like, and the PPCP degradable flexible film material has optimal performance indexes such as tensile strength, elongation at break and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The PPCP degradable flexible film material is characterized by being mainly prepared from the following raw materials in parts by mass:
2. the PPCP degradable flexible film material as claimed in claim 1, which is characterized by being mainly prepared from the following raw materials in parts by mass:
3. the PPCP degradable flexible film material of claim 1 or 2, characterized by: the plasticizer is acetyl tributyl citrate or epoxidized soybean oil, the chain extender is ADR-4468, the antioxidant is antioxidant 1010 or antioxidant AT168, the opening agent is silica or talcum powder, the anti-hydrolysis agent is carbodiimide or epoxy compound, and the anti-ultraviolet agent is ultraviolet absorbent UV-531.
4. A method for preparing the PPCP degradable flexible film material of claim 1, 2 or 3, comprising the steps of:
(1) Selecting raw materials PPCP, PPC and PBAT, and uniformly mixing a plasticizer, a chain extender, an antioxidant, an opening agent, an anti-hydrolysis agent and an anti-ultraviolet agent;
(2) Feeding the mixed raw materials into a homodromous parallel double-screw extruder for melting, homogenizing, extruding, cutting and granulating;
(3) And (5) film blowing by a film blowing machine to obtain the PPCP degradable flexible film material.
5. The method for preparing the PPCP degradable flexible film material according to claim 4, which is characterized in that: in the step (2), the parallel double-screw extruder is started up and heated to 160-170 ℃, materials are added, and the rotating speed of the main screw is regulated to be gradually increased to 30-50 r/min.
6. The method for preparing the PPCP degradable flexible film material according to claim 4, which is characterized in that: in the step (3), when a film blowing and casting integrated machine is adopted to blow films at 130-145 ℃, the temperature of a feeding section of the film blowing and casting integrated machine is firstly adjusted to 130 ℃, the temperature of a melting section is 140 ℃, the temperature of a homogenizing section is 145 ℃, heating is started, then material particles are poured into a hopper, and the rotating speed, the traction speed and the winding speed of a screw rod are set to blow films; wherein the screw rotating speed is 15-25 rpm, and the speed ratio of the traction speed to the winding speed is 1:1.15.
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