Environment-friendly degradable color master batch for thin film and preparation method of environment-friendly degradable color master batch

Abstract

The invention relates to an environment-friendly degradable color master batch for a film and a preparation method of the environment-friendly degradable color master batch, and belongs to the technical field of high polymer materials. The environment-friendly degradable color master batch for the thin film comprises the following components in parts by weight: 40-60 parts of modified poly (butylene succinate), 10-15 parts of titanium dioxide, 1-5 parts of an antioxidant, 0.1-1 part of a plasticizer and 1-5 parts of a dispersing agent, the environment-friendly degradable color master batch for the thin film prepared by the invention not only has a good high-temperature-resistant effect, but also has excellent tensile and bending-resistant effects.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to an environmentally friendly and degradable masterbatch for film and a preparation method thereof. Background Art

[0002] Masterbatch is a new type of colorant designed specifically for polymer materials. It can significantly improve the dispersion of pigments in finished products, ensure the chemical stability of the pigments and the stability of the finished products, while protecting operators from the health hazards of pigment powder. Its process is simple, easy to change colors, and effectively saves time and raw materials.

[0003] The main types of polyester masterbatches include PLA, PBS, PCL, PHA, etc. Among them, environmentally friendly polybutylene succinate is widely used as a thermoplastic plastic in packaging films, shopping bags, disposable tableware and other fields due to its good processing properties. However, the low tensile strength and impact strength of polybutylene succinate limit its wide application. In addition, the main chain of polybutylene succinate is simple and there are few long side chains, resulting in poor biodegradation rate, thermal stability and durability. Therefore, the research and development of excellent environmentally friendly and degradable masterbatches for films has important practical significance and application value. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides an environmentally friendly and degradable masterbatch for film and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An environmentally friendly and biodegradable masterbatch for film and a preparation method thereof, comprising the following raw materials in parts by weight: 40-60 parts of modified polybutylene succinate, 10-15 parts of titanium dioxide, 1-5 parts of an antioxidant, 0.1-1 parts of a plasticizer, and 1-5 parts of a dispersant;

[0007] The antioxidant is antioxidant 1010;

[0008] The plasticizer is ethylene bisstearamide;

[0009] The dispersant is polyethylene wax.

[0010] The modified polybutylene succinate is prepared by the following method:

[0011] Step A1: Diethanolamine and N,N-dimethylformamide were mixed and stirred, cooled in an ice bath at 0°C, and o-toluene isocyanate was added and mixed evenly. The temperature was raised to 70°C, reacted for 3 hours, washed, and dried for 24 hours to obtain a compound;

[0012] Furthermore, the usage ratio of diethanolamine, N,N-dimethylformamide, and o-toluene isocyanate is 5.45-10.91 g: 6-12 mL: 7.06-14.11 g;

[0013] First, the amino group of diethanolamine reacts with the isocyanate of o-toluene isocyanate to synthesize the compound;

[0014] Step A2: Succinic anhydride, the compound, and p-toluenesulfonic acid were uniformly mixed, stirred and reacted at 140°C for 30 minutes under a nitrogen atmosphere, then heated to 180°C, reacted for 3-3.5 hours, and cooled to room temperature to obtain an intermediate product;

[0015] Furthermore, the ratio of succinic anhydride, compound, and p-toluenesulfonic acid is 10-20.01 g: 0.05-0.1 mol: 0.21-1.09 g;

[0016] Secondly, the carboxyl group after the ring opening of succinic anhydride reacts with the hydroxyl group of the compound to obtain an intermediate product;

[0017] Step A3: The intermediate product and 1,4-butanediol were mixed uniformly, and tetra-n-butyl titanate and p-toluenesulfonic acid monohydrate were added under argon protection, and the mixture was reacted in a vacuum at 250° C. for 1 hour, cooled, filtered, and dried at 50° C. for 48 hours to obtain modified polybutylene succinate;

[0018] Furthermore, the usage ratio of the intermediate product, 1,4-butanediol, tetra-n-butyl titanate, and p-toluenesulfonic acid monohydrate is 0.1-0.2 mol: 0.1-0.2 mol: 0.5-0.7 g: 0.5-1 g;

[0019] Finally, the carboxyl group of the intermediate product reacts with the hydroxyl group of 1,4-butanediol to synthesize modified polybutylene succinate.

[0020] A method for preparing an environmentally friendly and biodegradable masterbatch for film, comprising the following steps:

[0021] S1. Mix titanium dioxide, antioxidant, plasticizer and dispersant, and stir at a speed of 1000-1500 r / min for 15-30 min to prepare a mixture;

[0022] S2. Evenly mix the modified polybutylene succinate and the compounding materials, stir at 80-90°C at a speed of 1000-1500 r / min for 2-3h, and then use a twin-screw extruder to adjust the temperature of each zone of the twin-screw to 110-120°C, 160-190°C, 180-200°C, 200-220°C, 210-230°C, 220-230°C, 230-250°C, 240-250°C, 250-260°C, 260-280°C, and a screw speed of 280-350rpm, extrude and granulate, and dry to obtain an environmentally friendly and biodegradable masterbatch for film.

[0023] Beneficial effects of the present invention:

[0024] The environmentally friendly and degradable masterbatch for the film of the present invention has good high temperature resistance and excellent tensile and bending resistance, thereby extending the service life of the material.

[0025] The modified polybutylene succinate prepared by the present invention significantly improves the thermal stability of environmentally friendly and degradable masterbatch for film by introducing urea bonds with high bond energy, thereby extending the service life of the material. At the same time, the urea bonds enhance the interaction force between polymer molecules, making the material less likely to break when subjected to external forces, thereby improving the tensile strength, bending strength and impact strength of the material and imparting good durability. In addition, the introduction of the urea bonds also optimizes the melt viscosity and processing temperature range of the polybutylene succinate, making it easier to perform processes such as injection molding and extrusion, thereby improving production efficiency and reducing processing costs. Furthermore, as a biodegradable plastic, the modified polybutylene succinate not only retains its original environmental protection characteristics, but also the modified polybutylene succinate prepared with succinic anhydride as a raw material can reduce crystallinity, increase degradation rate, and reduce pollution to the environment, thereby achieving a dual improvement in environmental friendliness and high performance. DETAILED DESCRIPTION

[0026] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0027] Example 1: A method for preparing an environmentally friendly and degradable masterbatch for film, comprising the following steps:

[0028] S1. Weigh the raw materials by weight: 40 parts of modified polybutylene succinate (prepared in this embodiment), 10 parts of titanium dioxide, 1 part of antioxidant, 0.1 part of plasticizer, and 1 part of dispersant; mix the titanium dioxide, antioxidant 1010, ethylene bisstearamide, and polyethylene wax, and stir at a speed of 1000 r / min for 15 minutes to obtain a mixture;

[0029] S2. The modified polybutylene succinate and the compounding material were uniformly mixed, stirred at 80°C at a speed of 1000 r / min for 2 h, and then a twin-screw extruder was used, and the temperatures of each zone of the twin-screw were adjusted to 110°C, 160°C, 180°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, and 260°C, and the screw speed was 280 rpm. The mixture was extruded into granules and dried to obtain an environmentally friendly and biodegradable masterbatch for film;

[0030] The modified polybutylene succinate is prepared by the following method:

[0031] Step A1: 5.45 g of diethanolamine and 6 mL of N,N-dimethylformamide were mixed and stirred, cooled in an ice bath at 0°C, and 7.06 g of o-toluene isocyanate was added and mixed evenly. The temperature was raised to 70°C and the reaction was carried out for 3 h. The mixture was washed and dried for 24 h to obtain the compound;

[0032] Step A2: 10 g of succinic anhydride, 0.05 mol of the compound, and 0.21 g of p-toluenesulfonic acid were mixed uniformly, stirred and reacted at 140° C. for 30 min under a nitrogen atmosphere, then heated to 180° C. for 3 h, and cooled to room temperature to obtain an intermediate product;

[0033] Step A3: 0.1 mol of the intermediate product and 0.1 mol of 1,4-butanediol were mixed evenly. Under argon protection, 0.5 g of tetra-n-butyl titanate and 0.5 g of p-toluenesulfonic acid monohydrate were added and mixed. The mixture was reacted in a vacuum at 250°C for 1 h. The mixture was cooled, filtered, and dried at 50°C for 48 h to obtain modified polybutylene succinate.

[0034] Example 2: A method for preparing an environmentally friendly and degradable masterbatch for film, comprising the following steps:

[0035] S1. Weigh the raw materials by weight: 50 parts of modified polybutylene succinate (prepared in this embodiment), 12.5 parts of titanium dioxide, 3 parts of antioxidant, 0.5 parts of plasticizer, and 3 parts of dispersant; mix the titanium dioxide, antioxidant 1010, ethylene bisstearamide, and polyethylene wax, and stir at a speed of 1250 r / min for 22 min to obtain a mixture;

[0036] S2. The modified polybutylene succinate and the compounding material were uniformly mixed, stirred at 85°C at a speed of 1250 r / min for 2.5 h, and then a twin-screw extruder was used, and the temperatures of each zone of the twin-screw were adjusted to 115°C, 175°C, 190°C, 210°C, 220°C, 225°C, 240°C, 245°C, 255°C, and 270°C, and the screw speed was 315 rpm. The mixture was extruded into granules and dried to obtain an environmentally friendly and biodegradable masterbatch for film;

[0037] The modified polybutylene succinate is prepared by the following method:

[0038] Step A1: 8.18 g of diethanolamine and 9 mL of N,N-dimethylformamide were mixed and stirred, cooled in an ice bath at 0°C, and 10.585 g of o-toluene isocyanate was added and mixed evenly. The temperature was raised to 70°C and the reaction was carried out for 3 h. The mixture was washed and dried for 24 h to obtain the compound;

[0039] Step A2: 15 g of succinic anhydride, 0.075 mol of the compound, and 0.65 g of p-toluenesulfonic acid were mixed uniformly, stirred and reacted at 140° C. under a nitrogen atmosphere for 30 min, then heated to 180° C. and reacted for 3.25 h, and then cooled to room temperature to obtain an intermediate product;

[0040] Step A3: 0.15 mol of the intermediate product and 0.15 mol of 1,4-butanediol were mixed evenly. Under argon protection, 0.6 g of tetra-n-butyl titanate and 0.75 g of p-toluenesulfonic acid monohydrate were added and mixed. The mixture was reacted in a vacuum at 250°C for 1 h. The mixture was cooled, filtered, and dried at 50°C for 48 h to obtain modified polybutylene succinate.

[0041] Example 3: A method for preparing an environmentally friendly and biodegradable masterbatch for film, comprising the following steps:

[0042] S1. Weigh the raw materials by weight: 60 parts of modified polybutylene succinate (prepared in this embodiment), 15 parts of titanium dioxide, 5 parts of antioxidant, 1 part of plasticizer, and 5 parts of dispersant; mix the titanium dioxide, antioxidant 1010, ethylene bisstearamide, and polyethylene wax, and stir at a speed of 1500 r / min for 30 min to obtain a mixture;

[0043] S2. The modified polybutylene succinate and the compounding material were uniformly mixed, stirred at 90°C at a speed of 1500r / min for 3h, and then a twin-screw extruder was used to adjust the temperatures of the twin-screw zones to 120°C, 190°C, 200°C, 220°C, 230°C, 230°C, 250°C, 250°C, 260°C, and 280°C, with a screw speed of 350rpm. The mixture was extruded into granules and dried to obtain an environmentally friendly and biodegradable masterbatch for film;

[0044] The modified polybutylene succinate is prepared by the following method:

[0045] Step A1: 10.91 g of diethanolamine and 12 mL of N,N-dimethylformamide were mixed and stirred, cooled in an ice bath at 0°C, and 14.11 g of o-toluene isocyanate was added and mixed evenly. The temperature was raised to 70°C and the reaction was carried out for 3 h. The mixture was washed and dried for 24 h to obtain the compound;

[0046] Step A2: 20.01 g of succinic anhydride, 0.1 mol of the compound, and 1.09 g of p-toluenesulfonic acid were mixed uniformly, stirred and reacted at 140° C. under a nitrogen atmosphere for 30 min, then heated to 180° C. and reacted for 3.5 h, and then cooled to room temperature to obtain an intermediate product;

[0047] Step A3: 0.2 mol of the intermediate product and 0.2 mol of 1,4-butanediol were mixed evenly. Under argon protection, 0.7 g of tetra-n-butyl titanate and 1 g of p-toluenesulfonic acid monohydrate were added and mixed. The mixture was reacted in a vacuum at 250°C for 1 h. The mixture was cooled, filtered, and dried at 50°C for 48 h to obtain modified polybutylene succinate.

[0048] Comparative Example: This comparative example is an environmentally friendly and biodegradable masterbatch for film. The difference from Example 3 is that an equal amount of polybutylene succinate is used instead of the modified polybutylene succinate prepared in Example 3, and the rest are the same.

[0049] Performance test: The films prepared in Examples 1-3 and the comparative example were treated with environmentally friendly degradable masterbatches, and the biodegradation rate was determined according to the standard GB / T19811-2005; the tensile properties were determined according to the standard GB / T1040.2-2006 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics"; the flexural strength was determined according to the standard GB / T1450.1-2005; and the elongation at break was determined according to the standard GB / T1040-2006. The test results are shown in Table 1 below:

[0050] Table 1

[0051] It can be seen from the test data in Table 1 that the environmentally friendly and degradable masterbatch for the film prepared by the present invention has good high temperature resistance. It can also be seen from the above table that the environmentally friendly and degradable masterbatch for the film prepared by the present invention has anti-stretching and bending effects, thereby extending the service life of the material.

[0052] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an environmentally friendly and degradable masterbatch for film, characterized in that: The specific steps include: S1. Weigh the raw materials by weight: 40-60 parts of modified polybutylene succinate, 10-15 parts of titanium dioxide, 1-5 parts of antioxidant, 0.1-1 parts of plasticizer, and 1-5 parts of dispersant; mix the titanium dioxide, antioxidant, plasticizer, and dispersant, and stir at a speed of 1000-1500 r / min for 15-30 minutes to prepare a mixture; S2. Evenly mix the modified polybutylene succinate and the compounding materials, stir at 80-90°C at a speed of 1000-1500 r / min for 2-3h, and then use a twin-screw extruder to adjust the temperature of each zone of the twin-screw to 110-120°C, 160-190°C, 180-200°C, 200-220°C, 210-230°C, 220-230°C, 230-250°C, 240-250°C, 250-260°C, 260-280°C, and a screw speed of 280-350rpm, extrude and granulate, and dry to obtain an environmentally friendly and biodegradable masterbatch for film.

2. The method for preparing an environmentally friendly and degradable masterbatch for film according to claim 1, characterized in that: The modified polybutylene succinate is prepared by the following method: Step A1: Diethanolamine and N,N-dimethylformamide were mixed and stirred, cooled in an ice bath at 0°C, and o-toluene isocyanate was added and mixed evenly. The temperature was raised to 70°C, reacted for 3 hours, washed, and dried for 24 hours to obtain a compound; Step A2: Succinic anhydride, the compound, and p-toluenesulfonic acid were uniformly mixed, stirred and reacted at 140°C for 30 minutes under a nitrogen atmosphere, then heated to 180°C, reacted for 3-3.5 hours, and cooled to room temperature to obtain an intermediate product; Step A3: The intermediate product and 1,4-butanediol were mixed evenly, and tetrabutyl titanate and p-toluenesulfonic acid monohydrate were added under argon protection, and the mixture was reacted in a vacuum at 250°C for 1 hour, cooled, filtered, and dried at 50°C for 48 hours to obtain modified polybutylene succinate.

3. The method for preparing an environmentally friendly and degradable masterbatch for film according to claim 2, characterized in that: Step A1: The ratio of diethanolamine, N,N-dimethylformamide, and o-toluene isocyanate is 5.45-10.91 g: 6-12 mL: 7.06-14.11 g.

4. The method for preparing an environmentally friendly and degradable masterbatch for film according to claim 2, characterized in that: In step A2, the usage ratio of succinic anhydride, compound, and p-toluenesulfonic acid is 10-20.01 g: 0.05-0.1 mol: 0.21-1.09 g.

5. The method for preparing an environmentally friendly and degradable masterbatch for film according to claim 2, characterized in that: In step A3, the usage ratio of the intermediate product, 1,4-butanediol, tetra-n-butyl titanate, and p-toluenesulfonic acid monohydrate is 0.1-0.2 mol: 0.1-0.2 mol: 0.5-0.7 g: 0.5-1 g.

6. The method for preparing an environmentally friendly and degradable masterbatch for film according to claim 1, characterized in that: The antioxidant is antioxidant 1010, the plasticizer is ethylene bisstearamide, and the dispersant is polyethylene wax.

7. An environmentally friendly and biodegradable masterbatch for film, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 6.

Images