WO2023104071A1 - Biodegradable composition and preparation method and application thereof - Google Patents

Abstract

The invention relates to a biodegradable composition and a preparation method and an application thereof. The preparation raw materials comprise a carbon dioxide-containing polymer, a polyester polymer material, and an auxiliary agent. The polyester polymer material has a melt index of 2-50g/10min. By means of blending and modifying raw materials, a biodegradable composition with mechanical performance, processing performance, and use performance meeting the actual application can be obtained. Furthermore, the prepared biodegradable composition has broad application prospects in plates, bowls, basins, folders, straws, shopping bags, garbage bags, packaging bags, mulching films, gloves, combs, toothbrush handles, knives, forks, stationery, cushioning packaging, heat preservation materials, etc.

Description

A kind of biodegradable composition and its preparation method and application

This application claims the priority of the Chinese patent application submitted to the China Patent Office on December 7, 2021 with the application number CN202111483937.5 and the title of the invention "a biodegradable composition and its preparation method and application", the entire content of which Incorporated in this application by reference.

technical field

The present invention relates to the technical field of C08L, and more specifically relates to a biodegradable composition and its preparation method and application.

Background technique

Carbon dioxide-containing polymer is a kind of propylene glycol phthalate-propylene carbonate copolymer developed on the basis of carbon dioxide copolymer. In practical applications, this amorphous polymer has played a greater role in the production and preparation of food packaging bags and shopping bags because of its good biodegradability and gas barrier properties. However, the brittleness of propylene glycol phthalate-propylene carbonate copolymer is relatively poor, and its performance still needs to be optimized for its specific use.

In order to optimize the performance of propylene glycol phthalate-propylene carbonate copolymer, there are some related researches at this stage, combining propylene glycol phthalate-propylene carbonate copolymer with other polyester polymers, without reducing biological While improving the degradation performance, the mechanical properties of the material are improved. At this stage, there are many ways to improve the mechanical properties of materials through the action of two different polymers. For example, a Chinese patent with the patent publication number of CN109177401A discloses a completely biodegradable blown film, which is prepared from polylactic acid and polyparaffin. Phthalic acid-adipate-butylene glycol ester is prepared with additives in order to change the biodegradation performance of the material, but how to make the material have transparency, biodegradation performance and mechanical properties at the same time, to develop a New materials are a challenge for researchers.

Contents of the invention

In view of this, the first aspect of the present invention provides a biodegradable composition, the preparation raw materials include carbon dioxide-containing polymers, polyester polymer materials and auxiliary agents;

The melt index of the polyester polymer material is 2-50g/10min, 190°C, 2.16Kg.

Further preferably, the melt index of the polyester polymer material is 2-25g/10min, 190°C, 2.16Kg.

More preferably, the melt index of the polyester polymer material is 2-10g/10min, 190°C, 2.16Kg.

More preferably, the melt index of the polyester polymer material is 5g/10min, 190°C, 2.16Kg.

In some preferred embodiments, the polyester polymer material includes polybutylene succinate.

Polybutylene succinate, melt index 5g/10min, 190°C, 2.16Kg, purchased from Shanghai Hotspot Engineering Plastics Co., Ltd.

In some preferred embodiments, the weight ratio of the carbon dioxide-containing polymer to the polyester polymer material is 1-99:99-1.

In some preferred embodiments, the weight ratio of the carbon dioxide-containing polymer to the polyester polymer material is 1: (1-10); preferably, the carbon dioxide-containing polymer and the polyester polymer material The weight ratio of the materials is 1:3.5.

In some preferred embodiments, the carbon dioxide-containing polymer is a propylene glycol phthalate-propylene carbonate copolymer.

Propylene glycol phthalate-propylene carbonate copolymer was purchased from Shandong United Innovative Materials Group.

In some preferred embodiments, the additives include compatibilizers, antioxidants, light stabilizers, pigments, plasticizers, lubricants, fillers, foaming agents, flame retardants, antistatic agents, At least one of the molding agents.

In some preferred embodiments, the additives include antioxidants and plasticizers.

Preferably, the antioxidant includes antioxidant 1076 and antioxidant 168.

Further preferably, the weight ratio of the antioxidant 1076 to the antioxidant 168 is 1:(0.5-2.5).

In some preferred embodiments, the plasticizer is tributyl citrate.

In some preferred embodiments, the compatibilizer is selected from at least one of isocyanate compatibilizers, epoxy compound compatibilizers, and oxazoline compatibilizers.

In some preferred embodiments, the compatibilizer includes glycidyl methacrylate, graft modified glycidyl methacrylate, hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate at least one of the

In some preferred embodiments, the graft modified glycidyl methacrylate is selected from polylactic acid grafted glycidyl methacrylate, polybutylene succinate grafted glycidyl methacrylate , At least one of polybutylene terephthalate adipate grafted with glycidyl methacrylate.

Further preferably, the graft-modified glycidyl methacrylate is polybutylene succinate grafted with glycidyl methacrylate.

The preparation method of polybutylene succinate grafted glycidyl methacrylate comprises the following steps:

Add polybutylene succinate, glycidyl methacrylate and benzoyl peroxide into the reaction vessel, mix at 100-150°C for 5-10 minutes to obtain polybutylene succinate graft Glycidyl methacrylate.

The weight ratio of polybutylene succinate, glycidyl methacrylate and benzoyl peroxide is 3:(0.5-2):0.1.

In some preferred embodiments, the weight of the compatibilizer is 0.1% to 20% of the total weight of the carbon dioxide-containing polymer and the polyester polymer material; preferably, the carbon dioxide-containing polymer and the polyester polymer 0.1-5% of the total weight of the material.

After a large number of creative experiments of the applicant, it was found that in this system, polybutylene succinate and propylene glycol phthalate-propylene carbonate were grafted with glycidyl methacrylate by polybutylene succinate. The compatibility between ester copolymers is greatly improved, and a uniform distribution state is formed at the two-phase interface of polybutylene succinate and trimethylene phthalate-propylene carbonate copolymer, when the prepared material When subjected to external tensile stress, it can quickly disperse and transfer the stress received by different phases, greatly improving its tensile properties;

Simultaneously, in the experiment process, the applicant found that the weight of the added compatibilizer can greatly improve the tensile properties of the prepared material when the weight of the added compatibilizer is 0.1-5% of the total weight of the carbon dioxide-containing polymer and the polyester polymer material, especially When the weight of the compatibilizer is 0.9% of the total weight of the carbon dioxide-containing polymer and the polyester polymer material, the strength of the interaction between it and the active groups existing in the system can be enhanced, and the additive antioxidant can be avoided 1. The escape of plasticizer on the surface of the product and the appearance of pulverization ensure its excellent mechanical properties and stability.

In some preferred embodiments, the raw materials for the preparation of the biodegradable composition include: 20-50% of carbon dioxide-containing polymers, 40-80% of polyester polymer materials, and the balance of additives to 100%. .

A second aspect of the present invention provides a method for preparing a biodegradable composition, comprising the following steps:

1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

2) Put the mixture into a melting and kneading device, mix for 5-30 minutes, then put it into a twin-screw extruder, extrude and granulate at 100°C-180°C to obtain the product.

The third aspect of the present invention provides an application of a biodegradable composition, which is used in the fields of daily necessities, office supplies, toys, packaging materials, and thermal insulation materials.

Beneficial effect: Compared with the prior art, the biodegradable composition provided by the present invention has the following advantages:

In the present invention, PPCP and PBS are blended and modified to obtain serialized PPCP/PBS compositions, so as to obtain biodegradable materials whose mechanical properties, processing properties and usable properties meet practical applications;

And the biodegradable composition prepared by the present invention can be used in plates, bowls, basins, folders, straws, shopping bags, garbage bags, packaging bags, mulch, gloves, combs, toothbrush handles, knives, forks, stationery, buffer packaging It has a great application prospect in the fields of thermal insulation materials and so on.

Detailed ways

Example 1

A biodegradable composition, prepared raw materials by weight percentage, including: 21% of carbon dioxide-containing polymer, 73.5% of polyester polymer material, and the balance of additives to 100%.

The carbon dioxide-containing polymer is propylene glycol phthalate-propylene carbonate copolymer, purchased from Shandong Lianxin Materials Group.

The polyester polymer material is polybutylene succinate, the melt index is 5g/10min, 190°C, 2.16Kg, purchased from Shanghai Hotspot Engineering Plastics Co., Ltd.

The auxiliary agents include compatibilizers, antioxidants and plasticizers.

The preparation raw materials in the auxiliary agent are calculated by weight percentage, including: 0.85% of compatibilizer, 2.15% of antioxidant, and 2.5% of plasticizer;

Described compatibilizer is polybutylene succinate grafted glycidyl methacrylate, and preparation method comprises the following steps:

Add polybutylene succinate, glycidyl methacrylate and benzoyl peroxide into the reaction vessel, mix at 100-150°C for 5-10 minutes to obtain polybutylene succinate graft Glycidyl methacrylate.

The weight ratio of polybutylene succinate, glycidyl methacrylate, and benzoyl peroxide is 3:1.2:0.1, and the amount of glycidyl methacrylate added is 1.2 g.

Polybutylene succinate, brand name FZ91PM, was purchased from Suzhou Sujin Plastic New Material Co., Ltd.

The antioxidant is antioxidant 1076 and antioxidant 168 in a weight ratio of 1:1.15.

Described plasticizer is tributyl citrate.

A preparation method of a biodegradable composition, comprising the following steps:

1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

2) Put the mixture into a melting and kneading device, mix for 20 minutes, then put it into a twin-screw extruder, extrude and granulate at 140°C to obtain the product.

Example 2

A biodegradable composition, prepared raw materials by weight percentage, including: 18% of carbon dioxide-containing polymer, 76.5% of polyester polymer material, and the balance of additives to 100%.

The carbon dioxide-containing polymer is propylene glycol phthalate-propylene carbonate copolymer, purchased from Shandong Lianxin Materials Group.

The polyester polymer material is polybutylene succinate, the melt index is 5g/10min, 190°C, 2.16Kg, purchased from Shanghai Hotspot Engineering Plastics Co., Ltd.

The auxiliary agents include compatibilizers, antioxidants and plasticizers.

The preparation raw materials in the auxiliary agent are calculated by weight percentage, including: 0.85% of compatibilizer, 2.15% of antioxidant, and 2.5% of plasticizer;

Described compatibilizer is polybutylene succinate grafted glycidyl methacrylate, and preparation method comprises the following steps:

Add polybutylene succinate, glycidyl methacrylate and benzoyl peroxide into the reaction vessel, mix at 100-150°C for 5-10 minutes to obtain polybutylene succinate graft Glycidyl methacrylate.

The weight ratio of polybutylene succinate, glycidyl methacrylate, and benzoyl peroxide is 3:1.2:0.1, and the amount of glycidyl methacrylate added is 1.2 g.

Polybutylene succinate, brand name FZ91PM, was purchased from Suzhou Sujin Plastic New Material Co., Ltd.

The antioxidant is antioxidant 1076 and antioxidant 168 in a weight ratio of 1:1.15.

Described plasticizer is tributyl citrate.

A preparation method of a biodegradable composition, comprising the following steps:

1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

2) Put the mixture into a melting and kneading device, mix for 20 minutes, then put it into a twin-screw extruder, extrude and granulate at 140°C to obtain the product.

Example 3

A biodegradable composition, prepared raw materials by weight percentage, including: 21% of carbon dioxide-containing polymer, 73.5% of polyester polymer material, and the balance of additives to 100%.

The carbon dioxide-containing polymer is propylene glycol phthalate-propylene carbonate copolymer, purchased from Shandong Lianxin Materials Group.

The polyester polymer material is polybutylene succinate, the melt index is 22g/10min, 190°C, 2.16Kg, purchased from Shanghai Hotspot Engineering Plastics Co., Ltd.

The auxiliary agents include compatibilizers, antioxidants and plasticizers.

The preparation raw materials in the auxiliary agent are calculated by weight percentage, including: 0.85% of compatibilizer, 2.15% of antioxidant, and 2.5% of plasticizer;

Described compatibilizer is polybutylene succinate grafted glycidyl methacrylate, and preparation method comprises the following steps:

Add polybutylene succinate, glycidyl methacrylate and benzoyl peroxide into the reaction vessel, mix at 100-150°C for 5-10 minutes to obtain polybutylene succinate graft Glycidyl methacrylate.

The weight ratio of polybutylene succinate, glycidyl methacrylate, and benzoyl peroxide is 3:1.2:0.1, and the amount of glycidyl methacrylate added is 1.2 g.

Polybutylene succinate, brand name FZ91PM, was purchased from Suzhou Sujin Plastic New Material Co., Ltd.

The antioxidant is antioxidant 1076 and antioxidant 168 in a weight ratio of 1:1.15.

Described plasticizer is tributyl citrate.

A preparation method of a biodegradable composition, comprising the following steps:

1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

2) Put the mixture into a melting and kneading device, mix for 20 minutes, then put it into a twin-screw extruder, extrude and granulate at 140°C to obtain the product.

Example 4

A biodegradable composition, prepared raw materials by weight percentage, including: 21% of carbon dioxide-containing polymer, 73.5% of polyester polymer material, and the balance of additives to 100%.

The carbon dioxide-containing polymer is propylene glycol phthalate-propylene carbonate copolymer, purchased from Shandong Lianxin Materials Group.

The polyester polymer material is polybutylene succinate, the melt index is 5g/10min, 190°C, 2.16Kg, purchased from Shanghai Hotspot Engineering Plastics Co., Ltd.

The auxiliary agents include compatibilizers, antioxidants and plasticizers.

The preparation raw materials in the auxiliary agent are calculated by weight percentage, including: 0.85% of compatibilizer, 2.15% of antioxidant, and 2.5% of plasticizer;

Described compatibilizer is glycidyl methacrylate;

The antioxidant is antioxidant 1076 and antioxidant 168 in a weight ratio of 1:1.15.

Described plasticizer is tributyl citrate.

A preparation method of a biodegradable composition, comprising the following steps:

1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

2) Put the mixture into a melting and kneading device, mix for 20 minutes, then put it into a twin-screw extruder, extrude and granulate at 140°C to obtain the product.

Example 5

A biodegradable composition, prepared raw materials by weight percentage, including: 21% of carbon dioxide-containing polymer, 73.5% of polyester polymer material, and the balance of additives to 100%.

The carbon dioxide-containing polymer is propylene glycol phthalate-propylene carbonate copolymer, purchased from Shandong Lianxin Materials Group.

The polyester polymer material is polybutylene succinate, the melt index is 5g/10min, 190°C, 2.16Kg, purchased from Shanghai Hotspot Engineering Plastics Co., Ltd.

The auxiliary agents include compatibilizers, antioxidants and plasticizers.

The preparation raw materials in the auxiliary agent are calculated by weight percentage, including: 0.85% of compatibilizer, 2.15% of antioxidant, and 2.5% of plasticizer;

Described compatibilizer is polybutylene succinate grafted glycidyl methacrylate, and preparation method comprises the following steps:

Add polybutylene succinate, glycidyl methacrylate and benzoyl peroxide into the reaction vessel, mix at 100-150°C for 5-10 minutes to obtain polybutylene succinate graft Glycidyl methacrylate.

The weight ratio of polybutylene succinate, glycidyl methacrylate, and benzoyl peroxide is 3:1.2:0.1, and the amount of glycidyl methacrylate added is 1.2 g.

Polybutylene succinate, brand name FZ91PM, was purchased from Suzhou Sujin Plastic New Material Co., Ltd.

The antioxidant is antioxidant 1076 and antioxidant 168 in a weight ratio of 1:0.5.

Described plasticizer is tributyl citrate.

A preparation method of a biodegradable composition, comprising the following steps:

1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

2) Put the mixture into a melting and kneading device, mix for 20 minutes, then put it into a twin-screw extruder, extrude and granulate at 140°C to obtain the product.

Performance Testing:

1. Tensile strength test: The biodegradable composition prepared in Examples 1-5 was used for the tensile strength test, the test method was referred to GB/T-1040.1-2006, and the test results were recorded in Table 1 below.

2. Test of elongation at break: The biodegradable composition prepared in Examples 1-5 was used for the test of elongation at break. The test method was referred to GB/T-1040.1-2006, and the test results were recorded in Table 1.

3. Biodegradation performance test: The biodegradation composition prepared in Examples 1-5 was used for the biodegradation performance test. The test method refers to GB/T19277, and the test results are recorded in Table 1.

Table 1 Test results

the	Tensile strength/MPa	Elongation at break/%	biodegradation/month
Example 1	25	150	9
Example 2	twenty two	100	9
Example 3	18	135	10
Example 4	15	95	12
Example 5	twenty four	138	14

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (24)

1. A biodegradable composition, characterized in that the preparation raw materials include carbon dioxide-containing polymers, polyester polymer materials and auxiliary agents;

   The melt index of the polyester polymer material is 2-50g/10min.
2. The biodegradable composition according to claim 1, characterized in that the melt index of the polyester polymer material is 2-25g/10min.
3. The biodegradable composition according to claim 2, characterized in that the melt index of the polyester polymer material is 2-10 g/10 min.
4. The biodegradable composition according to claim 3, characterized in that the melt index of the polyester polymer material is 5g/10min.
5. The biodegradable composition according to any one of claims 1-4, characterized in that, the polyester polymer material comprises polybutylene succinate.
6. The biodegradable composition according to claim 1, characterized in that the weight ratio of the carbon dioxide-containing polymer to the polyester polymer material is 1-99:99-1.
7. The biodegradable composition according to claim 1 or 6, characterized in that the weight ratio of the carbon dioxide-containing polymer to the polyester polymer material is 1: (1-10).
8. The biodegradable composition according to claim 7, characterized in that the weight ratio of the carbon dioxide-containing polymer to the polyester polymer material is 1:3.5.
9. The biodegradable composition according to claim 1 or 6, wherein the carbon dioxide-containing polymer is a propylene glycol phthalate-propylene carbonate copolymer.
10. The biodegradable composition according to claim 1, wherein the auxiliary agent includes compatibilizer, antioxidant, light stabilizer, pigment, plasticizer, lubricant, filler, foaming agent, retarder At least one of combustion agent, antistatic agent and release agent.
11. The biodegradable composition according to claim 10, wherein the compatibilizer is at least one selected from isocyanate compatibilizers, epoxy compound compatibilizers and oxazoline compatibilizers.
12. The biodegradable composition according to claim 10 or 11, wherein the compatibilizer comprises glycidyl methacrylate, graft modified glycidyl methacrylate, hexamethylene diisocyanate and At least one of 4,4-diphenylmethane diisocyanate.
13. The biodegradable composition according to claim 12, wherein the graft modified glycidyl methacrylate is selected from polylactic acid grafted glycidyl methacrylate, polybutylene succinate At least one of glycidyl methacrylate grafted and polybutylene terephthalate adipate grafted with glycidyl methacrylate.
14. The biodegradable composition according to claim 13, is characterized in that, the preparation method of described polybutylene succinate grafted glycidyl methacrylate comprises the following steps:

    Add polybutylene succinate, glycidyl methacrylate and benzoyl peroxide into a reaction vessel, and mix at 100-150°C for 5-10 minutes to obtain the polybutylene succinate Grafted glycidyl methacrylate.
15. The biodegradable composition according to claim 14, wherein the weight ratio of said polybutylene succinate, glycidyl methacrylate and benzoyl peroxide is 3:(0.5～2 ): 0.1.
16. The biodegradable composition according to claim 10, characterized in that the weight of the compatibilizer is 0.1-20% of the total weight of the carbon dioxide-containing polymer and the polyester polymer material.
17. The biodegradable composition according to claim 16, characterized in that the weight of the compatibilizer is 0.1-5% of the total weight of the carbon dioxide-containing polymer and the polyester polymer material.
18. The biodegradable composition according to claim 10, wherein the auxiliary agent includes an antioxidant and a plasticizer.
19. The biodegradable composition according to claim 10 or 18, wherein the antioxidant comprises antioxidant 1076 and antioxidant 168.
20. The biodegradable composition according to claim 19, wherein the weight ratio of the antioxidant 1076 to the antioxidant 168 is 1:(0.5-2.5).
21. The biodegradable composition according to claim 10 or 18, wherein the plasticizer is tributyl citrate.
22. The biodegradable composition according to claim 1, characterized in that, the preparation raw materials include, by weight percentage, 20-50% of carbon dioxide-containing polymers, 40-80% of polyester polymer materials, and supplementary additives to 100%.
23. A preparation method of the biodegradable composition according to any one of claims 1 to 22, characterized in that it comprises the following steps:

    1) pre-mixing carbon dioxide-containing polymers, polyester polymer materials and additives to obtain a mixture;

    2) Put the mixture into a melting and kneading device, mix for 5-30 minutes, then put it into a twin-screw extruder, extrude and granulate at 100°C-180°C to obtain the product.
24. An application of the biodegradable composition according to any one of claims 1 to 22, characterized in that it is used in the fields of daily necessities, office supplies, toys, packaging materials, and thermal insulation materials.