Degradable master batch

Abstract

The invention discloses a degradable master batch. The degradable master batch mainly comprises PBAT and a filler, and is characterized in that the filler is obtained by mixing and heating 2-acrylamido-2-methyl-1-propanesulfonic acid modified attapulgite, acrylic acid modified oil shale semicoke, maleic anhydride, alkali, polyvinyl alcohol, an initiator and a cross-linking agent in a solvent for reaction. By adopting the master batch disclosed by the invention, the production cost of the existing PBAT mulching film can be reduced, and the strength of the mulching film can be improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of thin film materials, and particularly relates to a degradable master batch for preparing a PBAT thin film. BACKGROUND

[0002] Polybutylene adipate terephthalate (PBAT) is a thermoplastic biodegradable plastic copolymerized from polybutylene adipate (PBA) and polybutylene terephthalate (PBT), which has the flexibility of PBA and the heat resistance of PBT, can be completely degraded within one year under composting conditions, and is widely used in agricultural thin films, but the existing commercially available PBAT mulch film has problems of low strength and high cost. SUMMARY

[0003] In view of the shortcomings of the existing PBAT mulch film, the application provides a degradable master batch, which can reduce the production cost of the PBAT mulch film and improve the strength of the mulch film.

[0004] To achieve the above-mentioned purpose, the application adopts the following technical scheme: A degradable master batch, which is mainly composed of PBAT and a filler, and characterized in that the filler is obtained by mixing and heating 2-acrylamido-2-methyl-1-propane sulfonic acid modified attapulgite, acrylic acid modified oil shale semi-coke, maleic anhydride, alkali, polyvinyl alcohol, an initiator and a crosslinking agent in a solvent.

[0005] Preferably, the content of the filler is 70-85 wt%.

[0006] Preferably, the mass ratio of the 2-acrylamido-2-methyl-1-propane sulfonic acid modified attapulgite to the acrylic acid modified oil shale semi-coke is 1:1-10:1.

[0007] Preferably, the amount of the maleic anhydride is 10-20 % of the total mass of the 2-acrylamido-2-methyl-1-propane sulfonic acid modified attapulgite and the acrylic acid modified oil shale semi-coke.

[0008] Preferably, the amount of the polyvinyl alcohol is 2-5 % of the total mass of the 2-acrylamido-2-methyl-1-propane sulfonic acid modified attapulgite and the acrylic acid modified oil shale semi-coke.

[0009] Preferably, the amount of the initiator is 0.5-2 % of the mass of the maleic anhydride.

[0010] More preferably, the initiator is ammonium persulfate.

[0011] Preferably, the amount of the crosslinking agent is 1-5 % of the mass of the maleic anhydride.

[0012] More preferably, the crosslinking agent is N, N'-methylenebisacrylamide.

[0013] Preferably, the amount of the base is 1-15% of the mass of the maleic anhydride.

[0014] More preferably, the base is sodium hydroxide.

[0015] Preferably, the temperature of the reaction is 75-90 degrees Celsius and the time is 1-3 hours.

[0016] Preferably, the 2-acrylamido-2-methyl-1-propane sulfonic acid modified palygorskite is obtained by stirring 2-acrylamido-2-methyl-1-propane sulfonic acid and palygorskite in a solvent for a certain time.

[0017] More preferably, the amount of 2-acrylamido-2-methyl-1-propane sulfonic acid is 2-5% of the mass of the palygorskite.

[0018] More preferably, the 2-acrylamido-2-methyl-1-propane sulfonic acid and palygorskite are stirred in a solvent for 1-3 hours.

[0019] Preferably, the acrylic acid modified oil shale semi-coke is obtained by spraying acrylic acid on the surface of the oil shale semi-coke and stirring for a certain time.

[0020] More preferably, the amount of acrylic acid is 10-25% of the mass of the oil shale semi-coke.

[0021] More preferably, the acrylic acid is sprayed on the surface of the oil shale semi-coke and stirred for 10-60 minutes.

[0022] A degradable film mainly composed of PBAT and the degradable master batch as described above, wherein the content of the degradable master batch is 35-40 wt%. DETAILED DESCRIPTION

[0023] The technical solutions of the present application are further described in detail below in combination with examples.

[0024] Example 1 1. 100g of palygorskite was homogenized at high speed in water, then 2g of 2-acrylamido-2-methyl-1-propane sulfonic acid was added to the slurry, and stirred for 2 hours, then filtered, dried, and crushed, and recorded as ATP-0.

[0025] 2. 100g of oil shale semi-coke was crushed, 10g of acrylic acid was sprayed on the surface, and then stirred at high speed for 20 minutes, and recorded as 3Y-0.

[0026] 3. Mix 80g ATP-0 and 20g 3Y-0, then add water to prepare a 20wt% aqueous solution by ultrasonic, cool to 4-10 degrees Celsius, then add maleic anhydride (15g) aqueous solution, and add 1.5g sodium hydroxide, stir for about 15 minutes, then add polyvinyl alcohol-1799 (3g) aqueous solution, initiator ammonium persulfate (0.2g) and crosslinking agent N,N'-methylene bisacrylamide (0.3g), immediately degas and heat to 80 degrees Celsius under nitrogen protection, react for 2 hours, then filter, dry, freeze and crush into 3000 mesh powder. Denoted as ATP-3Y-PLY.

[0027] 4. Mix 80g ATP-3Y-PLY and 20g PBAT after high-speed stirring, then single-screw granulation to prepare ATP-3Y-PLY / PBAT masterbatch.

[0028] Comparative Example 1 1. Homogenize 100g attapulgite in water at high speed, then add 2g coupling agent KH-550 to the slurry, stir for 2 hours, then filter, dry, and crush, denoted as ATP-0-D.

[0029] 2. Crush 100g oil shale semi-coke, then spray 10g acrylic acid onto its surface and stir for 20 minutes at high speed, denoted as 3Y-0.

[0030] 3. Mix 80g ATP-0-D and 20g 3Y-0, then add water to prepare a 20wt% aqueous solution by ultrasonic, cool to 4-10 degrees Celsius, then add maleic anhydride (15g) aqueous solution, and add 1.5g sodium hydroxide, stir for about 15 minutes, then add polyvinyl alcohol-1799 (3g) aqueous solution, initiator ammonium persulfate (0.2g) and crosslinking agent N,N'-methylene bisacrylamide (0.3g), immediately degas and heat to 80 degrees Celsius under nitrogen protection, react for 2 hours, then filter, dry, freeze and crush into 3000 mesh powder. Denoted as ATP-3Y-PLY-D1.

[0031] 4. Mix 80g ATP-3Y-PLY-D1 and 20g PBAT after high-speed stirring, then single-screw granulation to prepare ATP-3Y-PLY / PBAT-D1 masterbatch.

[0032] Comparative Example 2 1. Homogenize 100g attapulgite in water at high speed, then add 2g 2-acrylamido-2-methyl-1-propane sulfonic acid to the slurry, stir for 2 hours, then filter, dry, and crush, denoted as ATP-0.

[0033] 2. Crush oil shale semi-coke.

[0034] 3. Mix 80g ATP-0 and 20g oil shale semi-coke powder, then add water to prepare a 20wt% aqueous solution by ultrasonic, cool to 4-10 degrees Celsius, then add maleic anhydride (15g) aqueous solution, and add 1.5g sodium hydroxide, stir for about 15 minutes, then add polyvinyl alcohol-1799 (3g) aqueous solution, initiator ammonium persulfate (0.2g) and crosslinking agent N,N'-methylene bisacrylamide (0.3g), immediately degas and heat to 80 degrees Celsius under nitrogen protection, react for 2 hours, then filter, dry, and freeze and crush into 3000 mesh powder. Denoted as D-ATP-3Y-PLY-D2.

[0035] 4. Mix 80g ATP-3Y-PLY-D2 with 20g PBAT by high-speed stirring, then single-screw granulation to prepare ATP-3Y-PLY / PBAT-D2 masterbatch.

[0036] Application: Mix PBAT with ATP-3Y-PLY / PBAT masterbatch of Example 1 at a mass ratio of 60:40, stir uniformly, and blow film to prepare a degradable film with a thickness of 0.017mm.

[0037] Comparative Sample 1: Mix PBAT with ATP-3Y-PLY / PBAT-D1 masterbatch of Comparative Example 1 at a mass ratio of 60:40, stir uniformly, and blow film to prepare a degradable film with a thickness of 0.017mm.

[0038] Comparative Sample 2: Mix PBAT with ATP-3Y-PLY / PBAT-D2 masterbatch of Comparative Example 2 at a mass ratio of 60:40, stir uniformly, and blow film to prepare a degradable film with a thickness of 0.017mm.

[0039] The performance test method of the film refers to GB / T 35795-2017, and the results are shown in Table 1.

[0040] Table 1 Performance test results of different degradable films

[0041] Example 2 1. Homogenize 100g attapulgite in water at high speed, then add 3g 2-acrylamido-2-methyl-1-propane sulfonic acid to the slurry, stir for 2 hours, then filter, dry, and crush, denoted as ATP-0.

[0042] 2. Crush 100g oil shale semi-coke, then spray 15g acrylic acid onto the surface and stir for 20 minutes at high speed, denoted as 3Y-0.

[0043] 3. Mix 90g ATP-0 and 10g 3Y-0, then add water to prepare a 20wt% aqueous solution by ultrasonic, cool to 4-10 degrees Celsius, then add maleic anhydride (15g) aqueous solution, and add 1.5g sodium hydroxide, stir for about 15 minutes, then add polyvinyl alcohol-1799 (3g) aqueous solution, initiator ammonium persulfate (0.1g) and crosslinking agent N,N'-methylene bisacrylamide (0.15g), immediately degas and heat to 80 degrees Celsius under nitrogen protection, react for 2 hours, then filter, dry, freeze and crush into 3000 mesh powder. Marked as ATP-3Y-PLY.

[0044] 4. Mix 85g ATP-3Y-PLY with 15g PBAT after high-speed stirring, then single-screw granulation to prepare ATP-3Y-PLY / PBAT masterbatch.

[0045] Example 3 1. Homogenize 100g attapulgite in water at high speed, then add 5g 2-acrylamido-2-methyl-1-propane sulfonic acid to the slurry, stir for 3 hours, then filter, dry, and crush, marked as ATP-0.

[0046] 2. Crush 100g oil shale semi-coke, spray 20g acrylic acid on the surface, and stir for 30 minutes at high speed, marked as 3Y-0.

[0047] 3. Mix 50g ATP-0 and 50g 3Y-0, then add water to prepare a 20wt% aqueous solution by ultrasonic, cool to 4-10 degrees Celsius, then add maleic anhydride (10g) aqueous solution, and add 0.1g sodium hydroxide, stir for about 15 minutes, then add polyvinyl alcohol-1799 (2g) aqueous solution, initiator ammonium persulfate (0.2g) and crosslinking agent N,N'-methylene bisacrylamide (0.5g), immediately degas and heat to 75 degrees Celsius under nitrogen protection, react for 3 hours, then filter, dry, freeze and crush into 3000 mesh powder. Marked as ATP-3Y-PLY.

[0048] 4. Mix 70g ATP-3Y-PLY with 30g PBAT after high-speed stirring, then single-screw granulation to prepare ATP-3Y-PLY / PBAT masterbatch.

[0049] Example 4 1. Homogenize 100g attapulgite in water at high speed, then add 2g 2-acrylamido-2-methyl-1-propane sulfonic acid to the slurry, stir for 2 hours, then filter, dry, and crush, marked as ATP-0.

[0050] 2. 100g oil shale semi-coke was crushed, 25g acrylic acid was sprayed on the surface of the oil shale semi-coke, and high-speed stirring was performed for 40 minutes, which was recorded as 3Y-0.

[0051] 3. 60g ATP-0 and 40g 3Y-0 were mixed, water was added to prepare a 20wt% aqueous solution, which was cooled to 4-10 degrees Celsius, then maleic anhydride (20g) aqueous solution and 3g sodium hydroxide were added, stirring for about 15 minutes, then polyvinyl alcohol-1799 (5g) aqueous solution, initiator ammonium persulfate (0.2g) and crosslinking agent N,N'-methylene bisacrylamide (0.4g) were added, immediately degassed and heated to 90 degrees Celsius under nitrogen protection, and reacted for 2.5 hours, then filtered, dried, and frozen and crushed into 3000 mesh powder. It is recorded as ATP-3Y-PLY.

[0052] 4. 80g ATP-3Y-PLY was mixed with 20g PBAT by high-speed stirring, and single-screw granulation was performed to prepare ATP-3Y-PLY / PBAT masterbatch.

[0053] 5. PBAT and ATP-3Y-PLY / PBAT masterbatch were mixed and stirred uniformly at a mass ratio of 65:35, and a degradable film with a thickness of 0.017mm was prepared by film blowing.

[0054] Finally, it should be pointed out that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A biodegradable masterbatch, said biodegradable masterbatch mainly composed of PBAT and fillers, characterized in that: The filler is obtained by mixing and heating attapulgite modified with 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylic acid modified oil shale semi-coke, maleic anhydride, alkali, polyvinyl alcohol, initiator and crosslinking agent in a solvent.

2. The biodegradable masterbatch according to claim 1, characterized in that: The filler content is 70~85 wt%.

3. The biodegradable masterbatch according to claim 1, characterized in that: The mass ratio of the 2-acrylamido-2-methyl-1-propanesulfonic acid modified attapulgite to the acrylic acid modified oil shale semi-coke is 1:1 to 10:

1.

4. The biodegradable masterbatch according to claim 1, characterized in that: The amount of maleic anhydride used is 10-20% of the total mass of the 2-acrylamido-2-methyl-1-propanesulfonic acid modified attapulgite and acrylic acid modified oil shale semi-coke; The amount of polyvinyl alcohol used is 2-5% of the total mass of the 2-acrylamido-2-methyl-1-propanesulfonic acid modified attapulgite and acrylic acid modified oil shale semi-coke; The amount of alkali used is 1-15% of the mass of maleic anhydride; The amount of the initiator is 0.5-2% of the mass of the maleic anhydride; The amount of the crosslinking agent is 1 to 5% of the mass of the maleic anhydride.

5. The biodegradable masterbatch according to claim 1 or 4, characterized in that: The alkali is sodium hydroxide, the initiator is ammonium persulfate, and the crosslinking agent is N,N'-methylenebisacrylamide.

6. The biodegradable masterbatch according to claim 1, characterized in that: The reaction is carried out at a temperature of 75-90 degrees Celsius for 1-3 hours.

7. The biodegradable masterbatch according to claim 1, characterized in that: The 2-acrylamide-2-methyl-1-propanesulfonic acid modified attapulgite is obtained by stirring 2-acrylamide-2-methyl-1-propanesulfonic acid and attapulgite in a solvent for a certain period of time. Preferably, the amount of 2-acrylamide-2-methyl-1-propanesulfonic acid is 2-5% of the mass of attapulgite. More preferably, the stirring reaction time is 1-3 hours.

8. The biodegradable masterbatch according to claim 1, characterized in that: The acrylic acid-modified oil shale semi-coke is obtained by spraying acrylic acid onto the surface of the oil shale semi-coke and stirring for a certain period of time. Preferably, the amount of acrylic acid used is 10-25% of the mass of the oil shale semi-coke, and more preferably, the stirring time is 10-60 minutes.

9. A biodegradable film, mainly composed of PBAT and a biodegradable masterbatch as described in any one of claims 1 to 8, wherein the content of the biodegradable masterbatch is 35 to 40 wt%.

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