Interface interlocking reinforced PBAT / HDPE composite material as well as preparation method and application thereof

Abstract

The invention relates to the field of polymer composite materials, in particular to an interface interlocking reinforced PBAT / HDPE composite material and a preparation method and application thereof. The preparation method comprises the following steps: blending HDPE and mica powder according to a mass ratio by using a torque rheometer to obtain HDPEF, and blending PBAT and montmorillonite according to a mass ratio by using the torque rheometer to obtain PBATT; blending the HDPEF and the PBATT composite material by using a torque rheometer to obtain a PBATT / HDPEF composite material; then carrying out injection molding and tabletting, and storing at room temperature for 48 hours to obtain the interface interlocking reinforced PBAT / HDPE composite material. The tensile strength of the composite material provided by the invention is 31.08 MPa; the tearing strength is 115 N / mm; after degradation, the obvious condition that the inorganic filler is embedded in the interface can be observed.

Description

Technical Field

[0001] The present invention relates to the field of polymer composites, and particularly to an interface interlocking enhanced PBAT / HDPE composite material, its preparation method and application. Two kinds of polymer plastics with poor compatibility are enhanced by interface interlocking, and mica powder and montmorillonite are used as "zippers" to enhance the polymer composite material at the interface of PBAT / HDPE. Background Art

[0002] The compatibility between polymers and inorganic fillers or between polymers has always been a key issue in the research and development of polymer composites. Poor compatibility will lead to a decline in the mechanical strength, toughness reduction and shortened service life of the composite material. There are usually the following three methods to improve the compatibility or interfacial bonding force of the composite material: First, modify the inorganic filler or another polymer to make it meet the required hydrophilicity and hydrophobicity. Of course, it can also be modified by itself; Second, by adding a third component, which has relatively good compatibility with all other components, so as to achieve the purpose of improving the overall compatibility of the material; Third, by changing the interfacial structure to enhance the interfacial bonding force to achieve the purpose of improving compatibility. This enhancement method requires a very good understanding of the components and the interactions between the components, and the success rate is relatively low, but the mechanical enhancement effect after success is more obvious.

[0003] Herein, we utilize the reverse compatibility between materials to form a "zipper"-type interlocking structure at the interface by mutually adding inorganic fillers, and study the differences in interface interlocking enhancement of different components, providing a new strategy for interface interlocking enhanced composites, a new idea for the reuse of polymer waste, and a simple and cheap new way for the downgraded use of composites. Summary of the Invention

[0004] The present invention overcomes the deficiencies of the prior art and provides an interface interlocking enhanced PBAT / HDPE composite material. By utilizing the reverse compatibility between materials, a "zipper"-type interlocking structure is formed at the interface by mutually adding inorganic fillers, and the differences in interface interlocking enhancement of different components are studied, providing a new strategy for interface interlocking enhanced composites, a new idea for the reuse of polymer waste, and a simple and cheap new way for the downgraded use of composites.

[0005] To solve the above technical problems, the technical solution adopted by the present invention is: An interface interlocking enhanced PBAT / HDPE composite material is made of the following raw materials in parts by weight: poly(butylene adipate terephthalate) (PBAT) 10 - 60 parts, high density polyethylene (HDPE) 40 - 90 parts, mica powder 0 - 15 parts, montmorillonite 0 - 10 parts and not zero.

[0006] As a further limitation of the technical solution of the present invention, the parameter model of the high-density polyethylene is 5000S, and the parameter model of the polybutylene adipate terephthalate is 1002H.

[0007] As a further limitation of the technical solution of the present invention, the parameters of the mica powder are 5000 mesh, and the parameters of the powder montmorillonite are: 325 mesh, calcium-based, purity > 95%.

[0008] As a further limitation of the technical solution of the present invention, the polybutylene adipate terephthalate is replaced with biodegradable materials such as poly(decylene sebacate-co-butylene terephthalate) (PBSeT), polylactic acid (PLA), and polybutylene succinate (PBS); the HDPE is replaced with other non-degradable materials.

[0009] The present invention also provides a method for preparing the above-mentioned interfacial interlocking enhanced PBAT / HDPE composite material, comprising the following steps:

[0010] (1) Preparation of HDPEF composite material: Using a torque rheometer, blend the high-density polyethylene and mica powder in parts by weight, and store it in a dry place for later use after completion;

[0011] (2) Preparation of PBATT composite material: Using a torque rheometer, blend the polybutylene adipate terephthalate and montmorillonite in a mass ratio according to the parts by weight, and store it in a dry place for later use after completion;

[0012] (3) Preparation of PBATT / HDPEF composite material: Using a torque rheometer, blend the HDPEF and PBATT composite materials, and store it in a dry place for later use after completion;

[0013] (4) Inject and press the prepared PBATT / HDPEF composite material into a mold, cold press it with a pressure of 10 MPa for 3 minutes each time, and store it at room temperature for 48 hours to obtain the interfacial interlocking enhanced PBAT / HDPE composite material.

[0014] First, select two inorganic fillers, one with good compatibility with PBAT or HDPE and the other with poor compatibility, and then prepare composites with the inorganic filler with poor compatibility respectively; secondly, blend the prepared PBAT and HDPE composites again, and utilize the reverse compatibility between the matrix and the filler to prepare a composite material with interlocked interfaces; in addition, due to the enhanced interaction between the interfaces, the strength of the composite material is improved while the cost is reduced; finally, after the biodegradable PBAT biodegradable material is degraded, the composite material forms a porous internal structure, and the inorganic material is embedded in the pores, thus becoming a porous material that can purify water, providing a new idea for the recycling of waste polymer materials, enhancing incompatible matrices, and preparing porous polymer matrix water purification materials.

[0015] By utilizing the reverse compatibility between the polymer matrix and the inorganic filler, a PBAT / HDPE composite material with an interlocked interface effect is prepared, enabling a strong interfacial interaction to form between two polymer matrices with poor compatibility, improving the mechanical properties of the composite material while significantly reducing the cost; in addition, after the biodegradable material in the composite material is degraded, a porous polymer-based material is formed, and two inorganic water purification materials are embedded inside such pores; finally, a polymer-based composite material with excellent mechanical properties, low cost, and degradable use is prepared.

[0016] As a further limitation of the preparation method of the present invention, the blending condition in step (1) is blending at 200 °C at 60 rad / min for 10 min.

[0017] As a further limitation of the preparation method of the present invention, the blending condition in step (2) is blending at 180 °C at 60 rad / min for 10 min.

[0018] As a further limitation of the preparation method of the present invention, the blending condition in step (3) is blending at 200 °C at 60 rad / min for 10 min.

[0019] In addition, the present invention also provides the application of the above-mentioned interlocked interface enhanced PBAT / HDPE composite material in the preparation of packaging bags, garbage bags, lunch boxes, agricultural films, and mulch films.

[0020] The present invention also provides the application of the above-mentioned interlocked interface enhanced PBAT / HDPE composite material after the biodegradable component is degraded in water filtration, removal of heavy metals and non-ferrous metals.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The interfacial interlock enhanced PBAT / HDPE composite material prepared by the present invention is obtained by a stepwise melt blending method using reverse compatibility, with a non-biodegradable material HDPE, a biodegradable material PBAT, and two inorganic fillers (mica powder and montmorillonite). First, PBAT and HDPE are respectively blended with montmorillonite and mica powder with poor compatibility with themselves, and then the formed composite materials are blended again. An interfacial interlock enhanced PBAT / HDPE composite material is prepared through good reverse compatibility between the polymer matrix and the inorganic filler; second, a large proportion of inorganic fillers with water purification functions reduces the overall cost of the composite material significantly; in addition, the strategies of interfacial interlock and degradation into water purification materials provide new ideas for polymer waste, enhancing incompatible matrices, and preparing polymer matrix water purification porous materials.

[0023] 2. The degradation materials and inorganic fillers in the main raw materials used for the interfacial interlock enhanced PBAT / HDPE composite material prepared by the present invention can be appropriately adjusted according to the changes in the matrix material. Of course, the non-biodegradable polymer material can also be polymer waste.

[0024] 3. In the preparation process of the composite material of the present invention, a stepwise melt blending method is adopted, without high-energy-consuming treatment methods. The process is simple and easy for industrial production.

[0025] 4. The interfacial interlock formed by the inorganic filler used in the present invention enables the matrix with poor compatibility to form strong interfacial interaction forces, without chemical crosslinking, and has good mechanical property recovery and low cost.

[0026] 5. The biodegradable material PBAT adopted in the present invention has good toughness, which is beneficial to compensating for the lack of toughness caused by the large addition of inorganic fillers.

[0027] Experimental results show that for the interfacial interlock enhanced PBAT / HDPE composite material provided by the present application, when the mass ratio of PBATT / HDPEF is 2 / 8, its tensile strength is 31.08 MPa, an increase of 25.6%; the tear strength is 115 N / mm, an increase of 4.1%; the impact strength is 16.88 KJ / m 2 , and the MFR is 1.07 g / 10 min. After degradation, obvious inorganic fillers embedded in the interface can be observed. Description of the Drawings

[0028] Figure 1 It is a comparative diagram of the tensile strength of PBATT, HDPEF, PBAT / HDPE, and PBATT / HDPEF composite materials.

[0029] Figure 2Tear strength comparison chart of PBATT, HDPEF, and PBATT / HDPEF composites.

[0030] Figure 3 Impact strength comparison chart of PBATT, HDPEF, and PBATT / HDPEF composites.

[0031] Figure 4 Melt flow rate comparison chart of PBATT / HDPEF composites.

[0032] Figure 5 SEM result chart of PBATT / HDPEF composites after degradation. Specific implementation mode

[0034] The present invention will be further described below in conjunction with specific embodiments.

[0035] The present invention provides raw materials for interfacial interlocking enhanced PBAT / HDPE composites: poly(butylene adipate-co-terephthalate) (PBAT) is purchased from Jinhui Zhaolong High-Tech Co., Ltd.; high-density polyethylene (HDPE) is purchased from PetroChina Company Limited; mica powder is purchased from Henan Borun Foundry Materials Co., Ltd.; montmorillonite is purchased from Shanlin Shiyu Mine. Of course, all raw materials can also be purchased from other production areas.

[0036] Control Example 1

[0037] Use a torque rheometer to blend HDPE and mica powder with a mass ratio of 7:3 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample is labeled as HDPEF.

[0038] Control Example 2

[0039] Use a torque rheometer to blend PBAT and montmorillonite with a mass ratio of 4:1 at 180 °C at 60 rad / min for 10 min. After the experiment, the sample is labeled as PBATT.

[0040] Control Example 3

[0041] Use a torque rheometer to blend HDPE and PBAT with a mass ratio of 63:8 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample is labeled as PBAT / HDPE-1 / 9.

[0042] Control Example 4

[0043] Using a torque rheometer, HDPE and PBAT with a mass ratio of 7:2 were blended at 200 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBAT / HDPE-2 / 8.

[0044] Control Example 5

[0045] Using a torque rheometer, HDPE and PBAT with a mass ratio of 49:24 were blended at 200 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBAT / HDPE-3 / 7.

[0046] Control Example 6

[0047] Using a torque rheometer, HDPE and montmorillonite with a mass ratio of 7:3 were blended at 200 °C at 60 rad / min for 10 min, and the sample was labeled HDPET; PBAT and mica powder with a mass ratio of 4:1 were blended at 180 °C at 60 rad / min for 10 min, and the sample was labeled PBATF; using a torque rheometer, the PBATF and HDPET composite materials with a mass ratio of 2:8 were blended at 200 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBATF / HDPET-2 / 8.

[0048] Control Example 7

[0049] Using a torque rheometer, PBSeT and montmorillonite with a mass ratio of 4:1 were blended at 180 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBSeTT.

[0050] Control Example 8

[0051] Using a torque rheometer, HDPE and PBSeT with a mass ratio of 7:2 were blended at 200 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBSeT / HDPE-2 / 8.

[0052] Example 1

[0053] In the third step, using a torque rheometer, the PBATT and HDPEF composite materials with a mass ratio of 1:9 were blended at 200 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBATT / HDPEF-1 / 9.

[0054] Example 2

[0055] In the third step, using a torque rheometer, the PBATT and HDPEF composite materials with a mass ratio of 2:8 were blended at 200 °C at 60 rad / min for 10 min. The experiment was completed, and the sample was labeled PBATT / HDPEF-2 / 8.

[0056] Example 3

[0057] In the third step, a torque rheometer was used to blend the PBATT and HDPEF composites with a mass ratio of 3:7 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample was denoted as PBATT / HDPEF-3 / 7.

[0058] Example 4

[0059] In the third step, a torque rheometer was used to blend the PBATT and HDPEF composites with a mass ratio of 4:6 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample was denoted as PBATT / HDPEF-4 / 6.

[0060] Example 5

[0061] In the third step, a torque rheometer was used to blend the PBATT and HDPEF composites with a mass ratio of 5:5 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample was denoted as PBATT / HDPEF-5 / 5.

[0062] Example 6

[0063] In the third step, a torque rheometer was used to blend the PBATT and HDPEF composites with a mass ratio of 6:4 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample was denoted as PBATT / HDPEF-6 / 4.

[0064] Example 7

[0065] In the second step, PBAT was replaced with PBSeT, and other conditions remained unchanged. The sample was labeled as PBSeTT. In the third step, a torque rheometer was used to blend the PBSeTT and HDPEF composites with a mass ratio of 2:8 at 200 °C at 60 rad / min for 10 min. After the experiment, the sample was denoted as PBSeTT / HDPEF-2 / 8.

[0066] Test results:

[0067] Before testing, the prepared composite materials were injection-molded and pressed into tablets in a special mold (cold-pressed for 3 min each with a pressure of 10 MPa), and stored at room temperature for 48 h before measurement.

[0068] Tensile strength, tear strength, impact strength, MFR, XRD, and SEM were used to characterize the PBATT, HDPEF, PBAT / HDPE, PBATF / HDPET, and PBATT / HDPEF composites of Comparative Examples 1-8 and Examples 1-7. The results are shown in Table 1 and as Figures 1 to 5 shown.

[0069] Table 1: Test results of tensile strength, tear strength, impact strength and MFR of PBATT, HDPEF, PBSeTT, PBAT / HDPE, PBATF / HDPET, PBATT / HDPEF, PBSeTT / HDPEF composites

[0070]

[0071] The results show that Table 1 and Figure 1 The results indicate that the tensile strength of PBATT, HDPEF, PBSeTT, PBAT / HDPE, PBSeT / HDPE, PBATF / HDPET composites decreases due to the poor compatibility between the matrix and inorganic materials or polymers. However, when HDPEF and PBATT (or PBSeTT) are blended, the tensile strength increases significantly. Table 1 and Figure 2 The results show that the mass ratio of PBATT / HDPEF of 4:6 is the dividing line of tear strength, and the enhancement effect is shown when the mass ratio is 2 / 8, which is consistent with the enhancement result of tensile strength. Table 1 and Figure 3 The results show that due to the increase of PBAT, the melt flow index increases, which is due to the high melt index of PBAT. Table 1 and Figure 4 The results show that due to the gradual increase of the proportion of the toughening component PBAT, the impact strength shows a downward trend. Table 1 and Figure 5 The results show that PBAT in the PBATT / HDPE-2 / 8 sample is removed by enzymatic degradation method. Combining the results of tensile strength and tear strength, this proportion of the sample indeed shows the effect of interfacial interlocking. The results show that a new crystalline structure appears in the proportion of the composite material with the effect of interfacial interlocking.

[0072] As described above, it is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. An interfacial interlocking reinforced PBAT / HDPE composite material, characterized in that: The invention is prepared from the following raw materials in parts by weight: 10 to 60 parts of polybutylene terephthalate-adipate, 40 to 90 parts of high-density polyethylene, 0 to 15 parts of mica powder, and 0 to 10 parts of montmorillonite (not 0).

2. The interfacial interlocking reinforced PBAT / HDPE composite material according to claim 1, characterized in that: The parameter model of the high-density polyethylene is 5000S, and the parameter model of polybutylene terephthalate-adipate is 1002H.

3. The interfacial interlocking reinforced PBAT / HDPE composite material according to claim 1, characterized in that: The mica powder parameter is 5000 mesh, and the powder montmorillonite parameter is: 325 mesh, calcium base, purity> 95%.

4. The interfacial interlocking reinforced PBAT / HDPE composite material according to claim 1, characterized in that: Polybutylene terephthalate-adipate is replaced by polydecane sebacate-butylene terephthalate, polylactic acid, polybutylene succinate biodegradable materials; the HDPE is replaced by other non-degradable materials.

5. A method for preparing an interfacial interlocking reinforced PBAT / HDPE composite material according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) Preparation of HDPEF composite material: High-density polyethylene and mica powder were blended in a weight ratio using a torque rheometer and then stored in a dry place for later use; (2) Preparation of PBATT composite material: Polybutylene terephthalate-adipate and montmorillonite in a weight ratio were blended using a torque rheometer and then stored in a dry place for future use; (3) Preparation of PBATT / HDPEF composites: HDPEF and PBATT composites were blended using a torque rheometer and then stored in a dry place for later use; (4) The prepared PBATT / HDPEF composite material was injection molded and placed in a mold for tableting, and then cold pressed for 3 minutes at a pressure of 10 MPa, and stored at room temperature for 48 hours to obtain an interface interlocking reinforced PBAT / HDPE composite material.

6. The method for preparing an interfacial interlocking reinforced PBAT / HDPE composite material according to claim 5, characterized in that: The blending condition in step (1) is blending at 200° C. and 60 rad / min for 10 min.

7. The method for preparing an interfacial interlocking reinforced PBAT / HDPE composite material according to claim 5, characterized in that: The blending condition in step (2) is blending at 180° C. and 60 rad / min for 10 min.

8. The method for preparing an interfacial interlocking reinforced PBAT / HDPE composite material according to claim 5, characterized in that: The blending condition in step (3) is blending at 200°C and 60 rad / min for 10 min.

9. Use of an interfacial interlocking reinforced PBAT / HDPE composite material as claimed in claim 1 in the preparation of packaging bags, garbage bags, lunch box agricultural films and ground films.

10. A use of the biodegradable component in the interlocking reinforced PBAT / HDPE composite material as claimed in claim 1 in water filtration and removal of heavy metals and non-ferrous metals after degradation.

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