Preparation method of degradable titanium dioxide master batch

Abstract

A preparation method of a degradable titanium dioxide master batch relates to the field of high polymer materials, and the preparation process is as follows: firstly drying PBAT, PLA, PBS and PBSA, then mixing PBAT, PLA, PBS, PBSA, titanium dioxide, a chain extender, an antioxidant and a lubricant in a high-speed mixer, then placing the mixture in a twin-screw extruder for melt blending, water-cooling pelletizing and drying to obtain PBAT / PLA / PBS / PBSA / TiO2 composite master batch. And finally, carrying out film blowing on the master batch by using a high-speed film blowing machine to prepare the PBAT / PLA / PBS / PBSA / TiO2 composite film. Titanium dioxide is blended with PBAT, PLA, PBS and PBSA, the chain extender is added to improve the compatibility of the system, and the prepared composite master batch is biodegradable, excellent in performance and remarkable in whitening effect, can be applied to processing of various materials and is expected to replace non-degradable traditional plastics in part of fields.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a method for preparing a degradable titanium dioxide masterbatch. Background Art

[0002] Plastics made from petroleum-based polymers such as polyethylene, polyvinyl chloride, and polypropylene are cheap and have good performance. They have developed rapidly in the past few decades and are widely used in people's daily lives. However, these traditional plastics are difficult to degrade in the natural environment, not only polluting the soil, atmosphere, and water, but also endangering the health of humans and animals, causing serious "white pollution" problems. Therefore, as the demand for plastics continues to increase, it has become imperative to develop new types of degradable plastics.

[0003] Polylactic acid (PLA), as a highly anticipated polyester material, has the outstanding characteristic of being completely biodegradable, but its flexibility is poor and its texture is hard and brittle, which greatly restricts its expansion in practical application scenarios. In view of this, how to develop a film that has both excellent optical properties and good flexibility, can be bent and stretched at will without being easily damaged, and has excellent ductility, can be shaped into various forms according to different molding processes, and has high strength to ensure the durability of the product has become a key technical barrier that the present invention needs to overcome. Summary of the invention

[0004] The purpose of the present invention is to solve the above problems in the prior art and provide a method for preparing a degradable titanium dioxide masterbatch. The prepared masterbatch is biodegradable, has high whiteness and good performance, and can be applied to the processing of various materials.

[0005] In order to achieve the above object, the present invention adopts the following technical scheme:

[0006] A method for preparing a degradable titanium dioxide masterbatch comprises the following steps:

[0007] 1) Put PBAT (polybutylene adipate-terephthalate), PLA (polylactic acid), PBS (polybutylene succinate), and PBSA (polybutylene succinate-butylene adipate) into an oven for drying;

[0008] 2) Mix the dried PBAT, PLA, PBS, PBSA, titanium dioxide, chain extender, antioxidant, and lubricant in a high-speed mixer in proportion;

[0009] 3) placing the mixed material in a twin-screw extruder for melt blending, water cooling, pelletizing and drying to obtain the biodegradable titanium dioxide masterbatch;

[0010] Wherein, in step 2), the PBAT, PLA, PBS, PBSA, and titanium dioxide are calculated by weight as follows: 10 to 100 parts of PBAT, no more than 80 parts of PLA, no more than 80 parts of PBS, no more than 80 parts of PBSA, and 0.1 to 20 parts of titanium dioxide.

[0011] In step 2), the chain extender is 0.1-1.0 part, the antioxidant is 0.5-5 part, and the lubricant is 0.5-5 part.

[0012] In step 3), the temperature distribution from the feed section to the die of the twin-screw extruder is 120-180°C, 150-180°C, 160-190°C, 160-190°C, 160-190°C, 170-195°C, 170-195°C, 170-200°C, 170-200°C, and 170-200°C.

[0013] A degradable titanium dioxide masterbatch is prepared by the above preparation method.

[0014] The application of the degradable titanium dioxide masterbatch is used to prepare PBAT / PLA / PBS / PBSA / TiO 2 Composite film.

[0015] Specifically, the dried biodegradable titanium dioxide masterbatch was blown into film using a high-speed film blowing machine to obtain PBAT / PLA / PBS / PBSA / TiO 2 Composite film; the temperatures of the screw heating zones of the high-speed film blowing machine are 120-170°C, 160-180°C, 160-190°C, 170-200°C, and 160-200°C, respectively.

[0016] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0017] The present invention blends PBAT, PLA, PBS and PBSA, and adds different proportions and types of titanium dioxide to the blending system, and melt-extrudes and granulates the mixture through a twin-screw extruder to obtain a degradable titanium dioxide masterbatch. The film formed by blow molding has excellent mechanical properties and a significant whitening effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The tensile strength test results of different samples.

[0019] Figure 2 The elongation at break test results of different samples are shown in Figure 2.

[0020] Figure 3 The transmittance test results of different samples are shown in Figure 2.

[0021] Figure 4The haze test results of different samples. DETAILED DESCRIPTION

[0022] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments.

[0023] In the present invention, the chain extender is a high epoxy functional polymer HPC-3510P; the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 330, antioxidant 3114, antioxidant 245, and antioxidant 264; the lubricant is calcium stearate; titanium dioxide A is anatase titanium dioxide with a particle size of about 25 nm; and titanium dioxide B is rutile titanium dioxide with a particle size of about 25 nm.

[0024] Comparative Example 1

[0025] Take 50 parts of PBAT, 40 parts of PLA, 5 parts of PBS and 5 parts of PBSA, put them in a 60°C oven and dry them for 8 hours, then take out, take 0.5 parts of chain extender, 1 part of antioxidant and 1 part of lubricant, pour them into a high-speed mixer and mix them evenly, the mixing time is 5 minutes. Pour the mixture into a twin-screw extruder for melt blending, the feed speed is 2 rpm, the main engine speed is 70 rpm, the temperature distribution from the feed section to the die is 180°C, 185°C, 185°C, 190°C, 190°C, 195°C, 195°C, 200°C, 200°C, 200°C, water cooling after extrusion, pelletizing, and obtaining PBAT / PLA composite masterbatch. After the obtained masterbatch was dried, it was blown into film using a high-speed film blowing machine. The screw speed was 15 rpm, the temperatures of the screw heating zones were 170°C, 175°C, 180°C, 180°C, and 170°C, respectively. The pulling speed was 7 rpm, the winding speed was 8.5 rpm, and the film thickness was 50 μm to obtain a PBAT / PLA / PBS / PBSA composite film.

[0026] Example 1

[0027] Take 50 parts of PBAT, 40 parts of PLA, 5 parts of PBS and 5 parts of PBSA, put them in an oven at 60°C and dry them for 8 hours, then take out, take 0.5 parts of chain extender, 1 part of antioxidant, 1 part of lubricant and 10 parts of titanium dioxide A, pour them into a high-speed mixer and mix them evenly, and the mixing time is 5 minutes. Pour the mixture into a twin-screw extruder for melt blending, the feed speed is 2 rpm, the main engine speed is 70 rpm, and the temperature distribution from the feed section to the die is 180°C, 185°C, 185°C, 190°C, 190°C, 195°C, 195°C, 200°C, 200°C, 200°C, and 200°C. After extrusion, water cooling and pelletizing are performed to obtain PBAT / PLA / PBS / PBSA / TiO 2Composite masterbatch. The obtained masterbatch was dried and then blown into film using a high-speed film blowing machine. The screw speed was 15 rpm, the screw heating zone temperatures were 170°C, 175°C, 180°C, 180°C, and 170°C, the traction speed was 7 rpm, the winding speed was 8.5 rpm, and the film thickness was 50 μm. PBAT / PLA / PBS / PBSA / TiO 2 Composite film.

[0028] Example 2

[0029] Take 50 parts of PBAT, 40 parts of PLA, 5 parts of PBS and 5 parts of PBSA, put them in an oven at 60°C and dry them for 8 hours, then take out, take 0.5 parts of chain extender, 1 part of antioxidant, 1 part of lubricant and 15 parts of titanium dioxide A, pour them into a high-speed mixer and mix them evenly, and the mixing time is 5 minutes. Pour the mixture into a twin-screw extruder for melt blending, the feed speed is 2 rpm, the main engine speed is 70 rpm, and the temperature distribution from the feed section to the die is 180°C, 185°C, 185°C, 190°C, 190°C, 195°C, 195°C, 200°C, 200°C, 200°C, and 200°C. After extrusion, water cooling and pelletizing are obtained to obtain PBAT / PLA / PBS / PBSA / TiO 2 Composite masterbatch. The obtained masterbatch was dried and then blown into film using a high-speed film blowing machine. The screw speed was 15 rpm, the temperatures of the screw heating zones were 170°C, 175°C, 180°C, 180°C, and 170°C, respectively. The pulling speed was 7 rpm, the winding speed was 8.5 rpm, and the film thickness was 50 μm. PBAT / PLA / PBS / PBSA / TiO 2 Composite film.

[0030] Example 3

[0031] Take 50 parts of PBAT, 40 parts of PLA, 5 parts of PBS and 5 parts of PBSA, put them in an oven at 60°C and dry them for 8 hours, then take them out, take 0.5 parts of chain extender, 1 part of antioxidant, 1 part of lubricant and 20 parts of titanium dioxide A, pour them into a high-speed mixer and mix them evenly, and the mixing time is 5 minutes. Pour the mixture into a twin-screw extruder for melt blending, the feed speed is 2 rpm, the main engine speed is 70 rpm, and the temperature distribution from the feed section to the die is 180°C, 185°C, 185°C, 190°C, 190°C, 195°C, 195°C, 200°C, 200°C, 200°C, and 200°C. After extrusion, water cooling and pelletizing are performed to obtain PBAT / PLA / PBS / PBSA / TiO 2Composite masterbatch. The obtained masterbatch was dried and then blown into film using a high-speed film blowing machine. The screw speed was 15 rpm, the temperatures of the screw heating zones were 170°C, 175°C, 180°C, 180°C, and 170°C, respectively. The pulling speed was 7 rpm, the winding speed was 8.5 rpm, and the film thickness was 50 μm. PBAT / PLA / PBS / PBSA / TiO 2 Composite film.

[0032] Example 4

[0033] Take 50 parts of PBAT, 40 parts of PLA, 5 parts of PBS and 5 parts of PBSA, put them in an oven at 60°C and dry them for 8 hours, then take them out, take 0.5 parts of chain extender, 1 part of antioxidant, 1 part of lubricant and 20 parts of titanium dioxide B, pour them into a high-speed mixer and mix them evenly, and the mixing time is 5 minutes. Pour the mixture into a twin-screw extruder for melt blending, the feed speed is 2 rpm, the main engine speed is 70 rpm, and the temperature distribution from the feed section to the die is 180°C, 185°C, 185°C, 190°C, 190°C, 195°C, 195°C, 200°C, 200°C, 200°C, and 200°C. After extrusion, water cooling and pelletizing are performed to obtain PBAT / PLA / PBS / PBSA / TiO 2 Composite masterbatch. The obtained masterbatch was dried and then blown into film using a high-speed film blowing machine. The screw speed was 15 rpm, the temperatures of the screw heating zones were 170°C, 175°C, 180°C, 180°C, and 170°C, respectively. The pulling speed was 7 rpm, the winding speed was 8.5 rpm, and the film thickness was 50 μm. PBAT / PLA / PBS / PBSA / TiO 2 Composite film.

[0034] Example 5

[0035] Take 40 parts of PBAT, 50 parts of PLA, 5 parts of PBS and 5 parts of PBSA, put them in an oven at 60°C and dry them for 8 hours, then take out, take 0.5 parts of chain extender, 1 part of antioxidant, 1 part of lubricant and 20 parts of titanium dioxide A, pour them into a high-speed mixer and mix them evenly, the mixing time is 5 minutes. Pour the mixture into a twin-screw extruder for melt blending, the feed speed is 2 rpm, the main engine speed is 70 rpm, the temperature distribution from the feed section to the die is 180°C, 185°C, 185°C, 190°C, 190°C, 195°C, 195°C, 200°C, 200°C, 200°C, after extrusion, water cooling and pelletizing to obtain PBAT / PLA / PBS / PBSA / TiO 2Composite masterbatch. The obtained masterbatch was dried and then blown into film using a high-speed film blowing machine. The screw speed was 15 rpm, the temperatures of the screw heating zones were 170°C, 175°C, 180°C, 180°C, and 170°C, respectively. The pulling speed was 7 rpm, the winding speed was 8.5 rpm, and the film thickness was 50 μm. PBAT / PLA / PBS / PBSA / TiO 2 Composite film.

[0036] The PBAT / PLA / PBS / PBSA / TiO prepared in Comparative Example 1 (D1) and Examples 1 to 5 (S1 to S5) were 2 The composite film is tested for mechanical properties and optical properties. The specific test methods are as follows:

[0037] (1) Mechanical properties: Tested according to GB / T 1040.3-2006, the samples were cut into 100 mm pieces with a cutting knife. The rectangular specimen of 15 mm, the initial distance between the upper and lower clamps is 50 mm, the tensile speed is 50 mm / min, and the test results are shown in Figure 1 , Figure 2 .

[0038] (2) Optical properties: Tested according to GB / T 2410-2008, cut the sample into 50mm pieces with a cutting knife. 50mm square piece, measure the transmittance and haze parameters of the composite film, the test results are shown in Figure 3 , Figure 4 .

[0039] It can be seen from the test results that the film blown by the present invention has higher mechanical properties and better whitening effect. Combined with the test results of Comparative Example 1 and Examples 1 to 3, it can be seen that after adding titanium dioxide A, in terms of tensile strength, the longitudinal tensile strength of the film decreases as a whole, while the transverse tensile strength increases as a whole, and as the addition amount of titanium dioxide A increases from 10% to 20%, the tensile strength gradually decreases; in terms of ductility, after adding titanium dioxide A, the longitudinal and transverse elongation at break of the film both show a decrease, and as the addition amount of titanium dioxide A increases from 10% to 20%, the longitudinal elongation at break first increases slightly and then decreases, and the transverse elongation at break first decreases and then increases; in terms of optical properties, as the addition amount of titanium dioxide A in the film increases, the light transmittance of the film gradually decreases and the haze gradually increases, indicating that the whitening effect of titanium dioxide gradually increases.

[0040] Combining the test results of Example 3 and Example 4, it can be seen that the film with titanium dioxide B added exhibits better mechanical properties and whitening effect.

[0041] Combining the test results of Example 3 and Example 5, it can be seen that when the proportion of PBAT in the composite film decreases, the mechanical properties and whitening effect of the film also decrease.

Claims

1. A method for preparing a degradable titanium dioxide masterbatch, characterized in that: The following steps are involved: 1) Dry PBAT, PLA, PBS and PBSA in an oven; 2) Mix the dried PBAT, PLA, PBS, PBSA, titanium dioxide, chain extender, antioxidant, and lubricant in a high-speed mixer in proportion; 3) placing the mixed material in a twin-screw extruder for melt blending, water cooling, pelletizing and drying to obtain the biodegradable titanium dioxide masterbatch; Wherein, in step 2), the PBAT, PLA, PBS, PBSA, and titanium dioxide are calculated by weight as follows: 10 to 100 parts of PBAT, no more than 80 parts of PLA, no more than 80 parts of PBS, no more than 80 parts of PBSA, and 0.1 to 20 parts of titanium dioxide.

2. The method for preparing a degradable titanium dioxide masterbatch according to claim 1, characterized in that: In step 2), the chain extender is 0.1-1.0 part, the antioxidant is 0.5-5 part, and the lubricant is 0.5-5 part.

3. The method for preparing a degradable titanium dioxide masterbatch according to claim 1, characterized in that: In step 3), the temperature distribution from the feed section to the die of the twin-screw extruder is 120-180°C, 150-180°C, 160-190°C, 160-190°C, 160-190°C, 170-195°C, 170-195°C, 170-200°C, 170-200°C, and 170-200°C.

4. A degradable titanium dioxide masterbatch, characterized in that: Prepared by the preparation method according to any one of claims 1 to 3.

5. The use of a degradable titanium dioxide masterbatch according to claim 4, characterized in that: Used to prepare PBAT / PLA / PBS / PBSA / TiO2 composite films.

6. The use according to claim 5, characterized in that: The dried biodegradable titanium dioxide masterbatch was blown into film using a high-speed film blowing machine to prepare a PBAT / PLA / PBS / PBSA / TiO2 composite film.

7. The use according to claim 6, characterized in that: The screw heating zone temperatures of the high-speed film blowing machine are 120-170°C, 160-180°C, 160-190°C, 170-200°C, and 160-200°C, respectively.

Images